HU195637B - Crop yield increasing and plant growth regulating compositions and process for producing substituted nitro- and cyanoguanidine derivatives being their active ingredient - Google Patents

Abstract

Novel substituted phenyl and benzyl nitroguanidine and phenyl and benzyl cyanoguanidine compounds. Methods for increasing crop yield, inhibiting lodging of graminaceous crops, and inducing cytokinin-like responses in crop plants with said novel guanidine compounds and derivatives thereof, as well as methods for inhibiting deterioration and/or extending the shelf life of harvested fruit, vegetables, and ornamentals are disclosed.

Description

FIELD OF THE INVENTION The present invention relates to crop growth regulating and plant growth controlling compositions and to the preparation of novel substituted nitro- and cyanoguanidine derivatives thereof.

In particular, the present invention provides new substituted phenyl and benzyl nitroguanidine derivatives and novel substituted phenyl and benzyl cyanoguanidine derivatives. Although nitro- and cyanoguanidine derivatives are already known in the art, the compounds of the present invention are novel compounds.

It has now been found that the novel compounds of formula (V) are represented by the formula

W ₅ is hydrogen, fluorine or chlorine,

_X5 is hydrogen, halogen, alkyl of straight or branched C 1-4 alkyl, -CN, - NO _2, CN ₂ CI1, -OCFjCIII'i OD /, -OCIIFí, -CF _3, C 1-4 alkyl containing alkoxy, -COOH, -NH ₂ , -CH ₂ -COOC ₂ H _s , -CH ₂ N (CH ₃ ) ₂ , tetrahydro-2 H -pyran-2-yl, -OH, -C (OH) _{2 CF3} -SC1I _3, -OSO ₂ C 11 _3, COCll _3l N (C11 _{3) 2,} -COOCH ₃ or -CH ₂ oR ₃ group, and in the latter R ₃ is hydrogen or -CH ₃ radical,

Y _s is hydrogen or halogen or -OH, -OCH ₃ , -CH _3i -CF ₃ , -CH ₂ -COOH, -ocf ₂ chf ₂ , -OCH ₃ , -CH ₂ -N (CH ₃ ) ₂ ,

-CH ₂ NH ₂ , -CN, -NHCOCH ₃ or

-N (C ₂ II _s ) ₂ , or

X _s and Y _s together form a -0- Cl I ₂ 0- group,

Z ₅ represents hydrogen, halogen or -CH _3, -0CH _3, or -CF ₃ group,

R 4 is hydrogen or -CH ₃ , -C ₂ H _S , -CF ₃ , phenyl or benzyl,

R _s is hydrogen or -CH ₃ ,

R ₆ is -NO ₂ or -CN, m is 0, 1 or 2, and n is 0 or 1, and some of them are highly valuable plant growth regulators, thus increasing, among other things, the yield of certain crop plants, accelerate the ripening of cereals and prevent the deterioration of crops and ornamental plants already harvested.

Narrow classes of compounds of formula (V) include the novel nitro and cyanoguanidine derivatives of formula (I), (II) (III), and (IV). In the general formula (I)

X 1 is halogen or -COCH ₃ , -CN, -CH ₂ CN, -C (OH) ₂ CH ₃ , -OCHF ₂ , -ocf ₃ , -CH ₃ , -SCH ₃ , -CF ₃ , -COOH, -NH ₂ , -CH ₂ COOC ₂ H, -CII ₂ -N (Cl ₁₃ ) ₂ .

-OSO ₁ CH ₃ , -no ₂ , -ocf ₂ chf ₂ , -och ₃ , -N (CH ₃ ) ₂ , -COOCH ₃ or -CH ₂ OR ₃ , in which R _{3 is} hydrogen or -CH ₃ ,

Y 1 is hydrogen or halogen or -CH ₃ , CF ₃ , -CH ₂ -COOH, -OCF ₂ CHF ₂ ,

-OCH ₃ , Cl 12 NjCH ₅ V -Cl ₁₂ NH ₂ , -CN, -NHCO ₂ CH ₃ or -N (C ₂ H ₅ ) ₂ , or

Xi and Y together form -0 CH ₂ O-,

2 is hydrogen or halogen;

C1I _3, OCII3 or CF ₃ group,

R is hydrogen or CII3 group, with the proviso that (i) when is fluorine, chlorine or bromine atom or -CII ₃ or -0CH ₃ group and R is hydrogen, then Y, Z and different, are hydrogen simultaneously, and (ii) when X ₁ is chlorine and Z 1 and R are both hydrogen then Y ₂ is other than methyl.

Also included within the scope of the invention are tautomers and alkali metal salts of the compounds of the general formula (I).

In the general formula (II)

X ₂ is hydrogen or halogen or -OH, straight or branched C 1-4 alkoxy, -SCH ₃ , -OCF ₃ , -OBJ, straight or branched C 1-4 alkyl, 6-oxacyclobex- 1-yloxy or tetrabidro-2H-pyran-2-yl,

Y ₂ is hydrogen or fluorine,

Z ₂ represents a hydrogen or fluorine atom or - CI1 or -0CH _{3 3} group,

V ₂ is hydrogen or fluorine, m is 0, 1 or 2,

R ₂ is hydrogen or -CH ₃ , -C ₂ H ₅ , -CF ₃ , phenyl or benzyl, provided that (i) when m is 0 and R _{2 is} hydrogen or -CH ₃ , then W ₂ , X ₂ , Y ₂ and Z _{2 are} simultaneously different from hydrogen, and (ii) when tn is 1, R ₂ , W ₂ , X ₂ , Y ₂ and Z _{2 are} simultaneously different from hydrogen.

Also included within the scope of the invention are the tautomers and alkali metal salts of the compounds of formula (II).

(In formula III)

_X3 is halogcnatom or - OC11 _3, -Cll ₃ or -CF ₃ group,

Y ₃ is hydrogen, halogen, or -OH, and

Z ₃ is hydrogen or chlorine, with the proviso that when

195 637 (i) Y ₃ and Ζ ₃ can represent hydrogen at the same time, when X ₃ is -OCl ₃ , and (ii) X ₃ and Y ₃ are both chlorine, bromine or iodine, then Z ₃ is other than hydrogen. and (iii) when X ₃ is CH ₃ and Z ₃ is hydrogen, then Y ₃ is a chlorine atom.

The tautomers and alkali metal salts of the compounds of formula (III) are also included within the scope of the invention.

In the general formula (IV)

W ₄ is hydrogen or (luoratorn, and X ₄ represents a hydrogen or fluorine atom or a linear or branched chain containing one to four carbon atoms or alkoxy _t employing a straight or branched chain alkyl group having 1-4 carbon atoms, with the proviso that if W Means ₄ fluorine atoms then

X ₄ is hydrogen.

Also included within the scope of the invention are the tautomers and alkali metal salts of the compounds of formula (IV).

The alkali metal salts include the sodium and potassium salts.

Among the phenyl nitroguanidine derivatives of formula (I), the compounds of formula (Γ) may be prepared according to the invention as shown in Scheme A. In Scheme A, Y 1, X 1 and Z ₍ as previously defined and R 1 being C 1-4 alkyl). A similar reaction to Scheme A is described by McKay and Wright in Journal American Chemical Society, 71, 1968 (1949).

The reaction involves reacting an appropriate N-alkyl-N-nitroso-N'-nitro-guanidine of formula (VII) with an equimolar amount of an appropriate aniline derivative of formula (VI), wherein the substituents have the meanings given above. of the formula wherein R 'is as defined above, in a mixture of water and alcohol. The reaction mixture is then heated to about 40 ° C, a strong base such as sodium hydroxide is added and the alcohol is removed from the reaction mixture by evaporation. The remaining liquid is then filtered and the filtrate is acidified with a strong mineral acid, hydrochloric acid, to precipitate the product of formula (Γ).

The resulting compound of general formula (Γ) can be converted to the corresponding 2-methyl derivative of formula 1 ', i.e. the compound of formula I having R = CH _{3 at} elevated temperature by reaction with methyl iodide and silver oxide. or with sodium hydroxide as shown in Scheme B. In Scheme B, Xi, Yi and Z ₍ as previously defined.

The compounds R ₂ represents Compounds of formula (II) are hydrogen, m = 0, i.e. the compounds of formula (ΙΓ) can be prepared similarly to vegytiletekbez formula (Γ), except that the starting material, a substituted aniline a suitable substituted benzylamine derivative is used. Alternatively, compounds of formula (IP) may be prepared by reacting the corresponding benzylamine derivative with nitroguanidine as shown in Scheme C. The activated product is isolated by filtration and partitioned between a suitable solvent. In Scheme C, X ₂ , Y ₂ , Z ₂ and W ₂ are as previously defined. A reaction similar to that of Scheme C is described by Davis and Abrams in Proc. Am. Acad. Arts Sci., 61, 437 (1925).

The benzyl tetroguanidine derivatives of formula (II ') may also be prepared by reacting a benzylamine derivative of formula (VIII) with substantially equivalent amounts of 2-alkyl-1 (or 3) -nitro-2-thio-pseudocarbamide. . Optionally, a solvent such as ethanol may be used. A similar reaction is described by Fishbein and Gallahan in Journal American Chemical Society 76, 1877 (1954), using 2-methylethyl-3-ynro-2-thiopseudourea as pseudocarbamide, and is illustrated in Scheme D. In Scheme D, X ₂ , Y ₂ , Z ₂ and W ₂ are as previously defined.

The substituted phenyl and benzyl cyanoguanidine derivatives of the formulas (III) and (IV) can be readily prepared by dissolving or dispersing an appropriately substituted aniline derivative or benzylamine derivative in an equimolar amount of the resulting solution or suspension. with sodium dicyanamide. In practice, it is generally convenient to disperse sodium dicyanamide in water prior to mixing with the solution or dispersion of aniline or to disperse sodium dicyanamide in ethoxyethanol prior to reacting with benzylamine. This reaction is combined with (III) and (IV). using formula (V ') is shown in Scheme E. In this Scheme, the substituents have the meanings given below.

As mentioned above, the present invention relates to plant growth regulating compositions, including, inter alia, underground crops and ornamental plants, root crops, grass plants, fodder plants, tomatoes, tobacco, sunflower seeds, cotton, pumpkin fruits. These formulations are applied to the foliage of the plant to be treated or to the soil containing the seeds or other reproductive organs of the plant. The compositions of the present invention are generally a compound of formula (V) as an active ingredient

W ₅ is hydrogen, fluorine or chlorine,

X ₅ is hydrogen, halogen, or carbon containing alkyl, CN, -NO ₂ , -CH ₂ CN, -ocf ₂ chf ₂ , oce ₃ , -CF ₃ , 1-4 carbon atoms,

195 637 tetrahydro-2H-pyran-2-yl, C (O1I) ₂ CP _3, -SCI 1 _3, COCI l _3, -N _{(CH3) 2, 3} -COOC11 or _{-CH2 OR3} and in the latter R _{3 is} -CH ₃ ,

_And Y represents a hydrogen or halogen atom or ₍₅ Tl, group,

Z ₅ is hydrogen or halogen

-C1I ₃ - OCII ₃ or -CF ₃ group,

R ₄ is hydrogen or -CII _3, -C ₂ I1 _5, or -CF ₃ group,

R _s is hydrogen or -CH ₃ ,

R ₆ is -NO ₂ or -CN, m is 0 or 1, and n is 0 or 1 - or a tautomer or an alkali metal salt thereof.

Because of their yield enhancement activity, compounds of formula V wherein X ₅ is other than hydrogen, one of the above substituents, and Y ₅ , Z ₅ , n, R ₅ and R ₆ are as previously defined, m is 0 or are preferred. 1, R 4 is hydrogen and W ₅ is hydrogen. Are particularly preferred for their yield-enhancing effect of the phenyl derivatives were (V) of the formula wherein n is 0, _X5 is lialogénatom or -Cll _3, -CF _3, -OCF _3, -OCHF _2, -C (OH) ₂ CF ₃ -C0CH or _3, Y ₅ represents a halogen atom or -CH _3, or -OCH ₃ group, R ₅ is hydrogen hydrogen, halogen or -CH _3, Z ₅ represents hydrogen, R ₆ is -NO _2, and W ₅ is hydrogen, with the proviso that when X ₅ is chloro and _Z5 is hydrogen, _Y5 is other than methyl. The tautomers and alkali metal salts of these compounds are equally preferred.

In another preferred group of crop-yield-enhancing compounds in terms of the group of benzyl derivatives of formula (V) wherein n is 1, X ₅ is H, halogen, -CH ₃ or -OCH _3, Y _are hydrogen, fluoro, or -OCH _3, Z ₅ is hydrogen, R _s is hydrogen, R ₆ is -NO ₂ group, m is 0, R ₄ is hydrogen or -Cll ₃ and W ₅ are hydrogen.

In addition to their ability to regulate plant growth and increase yields, the compounds of formula V are unexpectedly harvested crops, in particular freshly harvested green fruits, vegetables and leafy ornamental plants, especially freshly harvested edible leafy greens such as lettuce, spinach, beetroot, to preserve the freshness of chard, leaf turnip or chicory and / or to prevent the deterioration of crops harvested.

For the preparation of the substituted phenolic nitroguanidine derivatives of formula (I) and the substituted benzylnitroguanidine derivatives of formula (II), the methods described above can also be used to prepare the nitroguanidine derivatives of formula (V), using aniline 4 or amine as starting material. The reaction is illustrated in Scheme F. In Scheme F, R ₆ is -NO _2, and R _s is hydrogen, migraine ,. m, n, W _5, X _s, Y ₅ and Z ₅ are as defined above.

Thus, it has been found that, in practical use, substituted guanidine stems of formula (V) are extremely effective in increasing yield when applied to an effective amount of the compositions comprising them on the foliage of the crop or on the soil, e.g. contains roots, bulbs, roots or their cuts. It has further been found that the compounds of formula (V) are particularly effective in the production of underground and ornamental plants, root crops, grass plants, fodder plants, tomatoes, cotton, cucumbers and fruits, in the form of biologically active compounds of formula (V) increase yield in both solid and liquid formulations.

Surprisingly, it has also been found that the soil containing the foliage of the aforementioned crop plants or their seeds or other propagating organs with a composition containing a substituted guanidine derivative of the formula V is 0.06-5.0 kg / ha, preferably 0.125 to 2 kg / ha. Treated at 0 kg / ha application rate, the size and / or number of tubers, tuberous roots, rhizomes, flower bulbs, bulbs, capsules, pumpkin fruits, stone fruits or fruit fruits is increased in the crop. It should also be noted that treating underground and ornamental and root crops with the same composition significantly improves the uniformity in size and shape of tubers, tuberous roots, rhizomes or bulbs. These results are particularly noticeable in potato-type crops (e.g., potato potatoes), in particular, for example (1) the greater number of potato tubers (2) the total weight of the potato tubers significantly increases, (3) the greater number of potato tubers and (4) a smaller number of potato tubers corresponding to size 2.

When applied to the harvested fruit, vegetable or ornamental crop to prevent spoilage and improve freshness or shelf life, the substituted guanidine derivatives of formula (V) are preferably utilized in the form of aqueous solutions of 0.01 to 800.0 p. p. m. containing the active ingredient and applied as dipping solutions or sprays to the fruit, vegetable or ornamental plant to be treated. In order to obtain the most favorable results, the fruit tuber, vegetable or ornamental plant to be protected against rapid deterioration from the substituted guanidine derivative of formula (V) as an active ingredient is 0.01 to 800 p. p. m. contains quantity-47

Spray with 195,637 small quantities of aqueous solution one or two days prior to harvest or immerse in such solution 24 hours after harvest. If multiple applications are not practicable, the harvested crop may be injected into the aqueous side of the active ingredient or may be prepared by such a solution shortly after harvest, preferably within 24 hours of harvest.

It has also been found that application of formulations containing substituted guanidine derivatives of formula (V) to foliage of grass plants such as rice at the time of garlands bloom prevents the rice from falling due to unfavorable weather conditions.

The remarkably unique plant growth regulating effect of the compositions of the present invention containing substituted guanidine derivatives of formula V is further demonstrated by changes in tobacco plants treated prior to ripening, preferably between the early seedling stage and the pr derivates. When tobacco plants with a height of about 5 to 125 cm are treated with a composition containing a substituted nitro or cyanoguanidine derivative of the formula (V) in an application rate of 0.025 to 2.50 kg / ha, preferably 0.1 to 0.3 kg / ha, the aging of more mature tobacco leaves is delayed or delayed until virtually all leaves of the treated plant begin to mature. Thus, harvesting of mature tobacco leaves can be accomplished in one or at most two cuts, whereas in the past there have been no unusual three or four cuts.

In addition to these advantages, it is noted that tobacco treated with a substituted nitro or cyanoguanidine derivative of formula (V) has an increased yield compared to an untreated plant.

While not wishing to be bound by any theory, it can be concluded from the experiments and from what has been said so far that the compounds of the present invention are true plant growth regulators as measured by a number of criteria. Thus, these compounds are not only capable of increasing yields, but can also exert regulatory effects in laboratory experiments.

These effects fall into at least three categories of results. Each of these categories of results is consistent with the conclusion that these compounds represent a novel class of cytokinins. Observed results include accelerated growth at translocation and increased chlorophyll biosynthesis in some tissues, together with reduced chlorophyll degradation (aging) in other tissues. These results suggest that the compounds of the invention would be capable of exerting other known effects of cltokinin on plant tissues in addition to those described below, and that these compounds could be utilized in a variety of other ways, such as metabolite storage organisms or tissue translocating to temporary storage sites, or to delaying aging and enhancing growth in certain plant tissues.

The compounds of the present invention have been shown to be capable of substituting the widely studied eitokinin, N ⁶ benzyladenine, for tissue stimulating activity in cytokinin-dependent soybean callus. The bioassay utilizing the cucumber ceviche extract disclosed below will be used to identify compounds which exert cytokinin-like activity. As with many hormone-type biological assays, the result obtained is logarithmically linear with respect to the concentration of the test compounds at which action occurs. The results obtained with the compounds of the invention are twofold, on the one hand, an increase in stimulation and, on the other hand, an increased rate of chlorophyll biosynthesis.

Growth stimulant was also tested in two additional assay systems. Thus, we were able to stimulate the growth of cotyledons in young radish seedlings, with little effect on the remainder of the seedlings (however, the length of the hair roots may be reduced) and faster growth on the leaf discs of Lima beans.

The compounds of the present invention also affect the translocation of sucrose from one site to another in a potato plant. Whole potato plants hydroponically treated with the compounds of the present invention at an early stage show early tuber development by increasing the size and weight of the tubers at half the period of gonadal development.

Another effect of the compounds of the invention was observed in inhibiting the aging of various plants. This is due to the persistence of chlorophyll in tissues that otherwise become yellow, indicating degradation of chlorophyll. This effect was observed when the compounds of the invention were applied to the foliage in patches or strips, for example on potato leaves, on leaf discs of hen or Romaine varieties, and on very young potato plants among the disadvantages.

The compounds of formula (V) are thus extremely effective in reversing the growth of a wide variety of crop plants and / or increasing yields. The following are examples of these crops:

Underground crops:

Solanum tuberosum L. - potato, Helianthus tuberosus - Jerusalem artichoke, Coloeasia antiguorum - tarragon, Coloeasia csculenta,

Allium cepa - onion

Allium sativum - garlic,

Allium porrum - leek,

Album choenoprasiim - chives and Album ascalonicutn - shallots;

195,637

Underground ornamental plants:

tubers, such as saffron or gladiolus, flower bulbs, such as tulips or hyacinths, and rootstocks, such as iris, canna or Solomon's seal;

Root crops:

Beta vulgar - beet, fodder beet and / or rnangold, Daucus carota - carrot,

Tragopogon porrifolius - lettuce beetle,

Pastinaca sativa - parsnips,

Raphanus sativus - radish,

Brassica rapa - white beet,

Brassica napobrassica - yellow carrot,

Ipomoea batatus,

Pioscroa alata,

Manihot esculenta - cassava,

Beta vulgar - beet;

Crop plants for lawns:

Hordeum vulgare - barley,

Triticum aestivum - wheat and Oryza sativa;

Gourds:

Cucumis sativus, L. - cucumber and Cucurbita pepo, L. - pumpkin;

Fruits:

Pyrus malus, L. - Alma; and

Marshmallow animals.

Gossypium hirsutum - cotton, and

Lycopersicom esculeutum - Tomato.

It has further been found, surprisingly, that certain (V) nitro and cyanoguanidine derivatives of the formula - for example, those (V) wherein Y ₅ and W ₅ is hydrogen, mígZ _s and are X ₅ is halogen and R _4, R _s , m and n are as previously defined - active in rice (Oryza sativa), sunflower (Helianthus annus L.), alfalfa (Medicago sativa I), forage grasses (e.g. Agrostis spp., Bromus spp., Dactylis spp. And Pheileum spp.) And tobacco (Nicotiana tobacum L.). When applied to the tobacco plants prior to cutting the apex of the plant, preferably when the plants are between about 5 cm and 140 cm in height, said nitro- and cyanoguanidines are capable of inhibiting the aging of the lower, more mature canopy leaves. younger leaves on the upper part of the stems of plants are also ripe for harvest. This treatment has great benefits for farmers, as the number of leaf pickings can be reduced to full harvest. In addition, the tobacco obtained from the plants so treated is of a more uniform quality than untreated tobacco.

A further advantage of the aforementioned compounds of formula (V) is that, when used in rice or sunflower, they increase the stiffness and / or diameter of the stalk, thus preventing the harmful tilting of these crop plants.

The most preferred compounds that provide the beneficial changes described above in crop plants and crop yields include the following:

I-Nitro-3- (3-Trifluoromethyl-methylthiazole-phenyl) - guanidine; l- (3,4-Dichlorophenyl) -3-nitroguanidine; i

- (3-Chlorophenyl) -3-nitroguanidine;

- (3,5-Dichlorophenyl) -3-nitroguanidine;

'(4-Chloro-3-trifluoromethyl-phenyl) -3-nitro-guanidine; i-Nitro-3- (3,5-xyl) gthianidine; ! - (4-bromo-3-nietjl-phenyl) -3-nitroguanidine; 1-Nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine;

1- (3-Chloro-4-fluoro-phenyl) -3-nitro-guanidine;

- (3-Acetylphenyl) -3-trio-guanidine; l- (3-Methoxybenzyl) -3-nitroguanidine;

- (3,5-dichloro-phenyl) -l-methyl-3-nitroguanidine;

- ('amino 3- (3-1-yl) -4-fluoro-1'-enyl) guanidine; - (3-chloro-4-fluoro-phenyl) -3-cyano-guanidine;

-Cyano-3- (3,5-dichlorophenyl) guanidine;

- (3-Chloro-4-hydroxyphenyl) -3-nitroguanidine; 1- (3-Melylbenzyl) -3-trio-guanidine; : Cyano-3- (3-was allowed to react-benzyl) guanidine;

Nitro-3-veratrylguanidine;

] - (3-Fluorobenzyl) -3-nitroguanidine;

] - (4-fluorobenzyl) -3-nitroguanidine;

l- (3-Bromophenyl) -3-nitroguanidine;

l-Nitro-3- (3,4,5-trichlorophenyl) guanidine;

l- (3-Bromophenyl) -3-cyanoguanidine;

1-Cyano-3- (3-trifluoromethylphenyl) guanidine; J-Benzyl-3-ciaiip guanidine;

- (3-iodo-phenyl) -3-nitro-guanidine;

-Nitro-3- (2,2,2-trifluoro-1,1-dihydroxy-ethyl) -teryl guanidine;

l- (4-Fluoro-3-methyl-feni1) -3-nitroguanidine;

Nitro-3- (3,4-xylyl) guanidine;

l- (3-Methoxymethyl-phenyl) -3-nitroguanidine;

l-Benzyl-3-nitroguanidine;

l- (4-Chloro-3-methyl-phenyl) -3-nitroguanidine; 1- [3- (Difluoromethoxy) phenyl] -3-nioguanidine;

Nitro-3- (3-propoxy-benzyl) guanidine; l- (alpha-methylbenzyl) -3-nitro-gnanidin;

- (2-Fluoro-5-methylt-butyzyl) -3-nitroguanidine;

(2-1 Hloro-5-luctoxybenzyl) -3-ni troguanidine, and 1-Ni tri-3- (3-trifluoromethoxy-phenyl) guanidine.

Preferably, the compounds of the present invention can be formulated as solid or liquid compositions which can then be dispersed in a liquid or solid diluent prior to application to vegetation or soil. These formulations may be formulated, for example, as liquid concentrates, emulsifiable concentrates, wettable powder formulations, dusting agents, powder concentrates and granular formulations.

A typical liquid concentrate can be prepared by grinding about 46% by weight of a guanidine compound of the invention with about 0.4% by weight of colloid

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195,637 niagnesin-aluminum-aluminosilicate, about 1.5% by weight of naphthalene-formaldehyde condensate, about 8% by weight of polyethylene glycol, about 0.1% by weight of nonylphenol-ethylene oxide condensate (9-1 mole of ethylene). oxide), about 0.1% by weight of a dispersant (e.g., sodium lignosulfonate), about 0.07% by weight of citric acid, about 46% by weight of water, and about 0.06% by weight of xanthan gum. The concentrate thus obtained is then dispersed in water and used as a liquid spray.

Another liquid concentrate may be prepared by mixing or milling about 40% by weight of the gnanidine slag of the invention, about 0.40% by weight of colloidal magnesium aluminium silicate, about 1.50% by weight of polymerized alkylnaphthalenesulfonic acid sodium salt, about 8.0% by weight. propylene glycol, about 0.1 wt% ethoxylated octylphenol, about 0.1 wt% nonylphenoxy-polyethoxyethanol, about 0.07 wt% citric acid, about 0.06 wt% xan dan resin, about 0.10 wt% % paraformaldehyde and about 49.77% water,

Emulsifiable concentrates may be prepared by dissolving about 10% by weight of the guanidine derivative of the invention in about 38% by weight of N-methylpyrrolidone, about 35% by weight of substituted benzene and about 10% by weight of a spreading activator (alkylaryl polyoxyethylene glycol, free fatty acid and containing about 7% by weight of a nonionic surfactant such as octylphenoxy-polyethoxyethanol or nonyl-phenoxy-polyethoxyethanol. This concentrate is dispersed in water and used as a liquid spray. It can be applied, without dilution, to particulate carriers, such as corncob, kaolin or attapulgite, to provide a granular formulation for treating the soil in which any of these crop plants will grow.

Emulsifiable concentrates may also be prepared by dissolving about 11% by weight of the active compound of the invention in a mixture of about 57% by weight of N-methylpyrrolidone, about 24% by weight of octyl alcohol, and about 8% by weight of polyethoxylated turkish red oil.

Typical wettable powder formulations can be prepared by grinding about 20-45% by weight of a finely divided carrier (e.g., kaolin, bentonite, diatomaceous earth or attapulgite), about 45-80% by weight of the invention. about 2-5% by weight of a dispersing agent (e.g., sodium lignosulfonate) and about 2-5% by weight of a nonionic surfactant (e.g., octylphenoxy-polyethoxyethanol or nonyl-phenoxy-polyethoxy-ethanol). Such a composition is generally dispersed in water for use as a liquid spray.

Advantageously, the active compounds of the invention may be formulated as aqueous sprays or dipping aqueous liquids of about 0.01 to 800.0 p. ρ. m. containing the active ingredient. Such compositions can be used, for example, to treat harvested fruits, vegetables, and ornamental plants to prevent their deterioration or aging.

The invention is further illustrated by the following embodiments.

1. Preparation of pclda 1-Nitro-3- (3,4,5-trichlorophenyl) guanidine

To a suspension of 3.3 g (0.0225 mol) of N-methyl-N-nitroso-N'-nitroguanidine in 200 ml of 50% aqueous ethanol was added 5.0 g (0.025 mol) of 3,4,5-trichloroaniline. and the resulting reaction mixture was maintained at 40 ° C for 72 hours and then treated with one molar equivalent of sodium hydroxide to decompose excess N-methyl-N-nitroso-N'-nitroguanidine. The reaction mixture was filtered and the filtrate was acidified with concentrated hydrochloric acid. 1.6 g of a yellow precipitate are obtained, which is recrystallized. The product (1.4 g), m.p. 209.5 ° C (dec.).

By proceeding as described above or as shown in Scheme A, but using an appropriately substituted aniline halide instead of 3,4,5-trichloroaniline and appropriately selecting the heating time, the compounds of formula (Γ) listed in Table 1 can be prepared. .

Table I Compounds of formula (1)

X, Y. z, Melting point fO F H H 172-174 cl II II 162-163 Br H H 180-181 I H H 183-186 CF, H H 154.5-155.5 ch ₃ H 11 122-124 ch ₂ cn H 11 165-167 ch ₂ and ₃ H H 106-107.5 ch ₂ oh 11 H 138-140 COC, H II I58-160 -C (OH) ₂ -CF ₃ II H 172-174 sch ₃ H H 155-157 OCHF ₂ H H 122-124 OCF, II II 135 136.5 OCF ₂ CHF ₂ H yl 158-160 OCH, H H 151.5 to 153.5 OC ₂ H _s H H 137.5 to 139 CN H H 207-208 from ₂ H H 194-196 H H H N (CH ₃ ) ₂ H H 158-159.5 cooch ₃ H H 173-175 cl F H 171-173 cl cl H . 155-156.5 cl ch ₃ H 176-177

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195,637

Continuation of Table I

X, y, Z, Melting point (° C) CF ₃ 1 II 168,170 cf ₃ cl H 212-213 ch ₃ F H 182-183.5 ch ₃ Br H 182-183 ch ₃ cl H 196.5 to 198 ' cii ₃ CII ₃ II 161 to 162.5 cl H cl 218-219 Br H Br 243 (decomposes) Br H ch ₃ 201-203 ch ₃ H ch ₃ 188-189 and ₃ H cf ₃ 152-154 cf ₃ H cf ₃ 224-226 and ₃ H OCH ₃ 208-209 cl cl cl 210 (decomposes) COOH H H 245-47 oc ₆ h ₅ H H 138-139.5 H Br H 189-191 II cf ₃ II 170-72 11 ClIjCOOll 11 199 to 200.5 H ocf ₂ chf ₂ H 152-53.5 in the purified f II 171-72 cl ch ₃ o H 185.5 to 186.5 nh ₂ ch ₃ 11 170.5 to 172.5 ch ₃ ch ₃ ch ₃ 207-09

Example 2

Part A Preparation of 1- (3,5-Dichlorophenyl) -2-methyl-3-nitroc-guanidine (Scheme G) Nitroguanidine (0.008 mol) and silver oxide (0.92 g, 0.004 mol) to a mixture of 10 m! methyl iodide is added and the suspension thus obtained is refluxed. After 2 hours, the black suspension gradually turns yellow. It is then cooled to room temperature and filtered through diatomaceous earth. After evaporation in vacuo, the crude product obtained is recrystallized from dictylether / tetrahydrofuran to give 1.6 g (76%) of a white solid, m.p. 136-138 ° C. This procedure also provides 1-methyl-3-nitro-1- (3-trifluoromethyl-4-fluorophenyl) guanidine, m.p. 169-171 ° C.

Part B] - (4-Bromo-3-methyl-phenyl) -1-methyl-3-nitro-anidine (Scheme H)

To a homogeneous mixture of phenyl nitroguanidine (3.0 g, 0.011 mol) in ethanol / water (5: 1) was added 0.94 ml of 50% aqueous sodium hydroxide solution (0.012 mol), followed by 4.79 ml (10.9 g, 0.077 mol) of methyl iodide. The reaction mixture was stirred at 25 ° C for 22 hours, and the white precipitate was filtered off, washed with water and recrystallized from ethanol to give 2.35 g (74.6%) of pure product, m.p. · C.

Part C

Preparation of -Benzyl-1-methyl-3-nitroguanidine (Scheme I)

To a suspension of MNNG (10.0 g, 0.068 mol) in ethanol / water (1: 1) at 25 ° C was added dropwise 9.89 g (0.082 mol) of N-methylbenzylamine. Over the next 15 minutes, an exothermic reaction occurs gradually and the temperature rises to 44 ° C. After stirring at room temperature for 42 hours, the resulting white slurry was filtered and the filtered white precipitate (7.13 g) was recrystallized from hexane / ethanol to give 6.06 g (43.0%) of pure product as a white crystalline solid, m.p. 103-107 ° C.

Example 3 Preparation of 1- (3-fluorobenzyl) -3-nitroguanidine

To a suspension of 8.33 g (0.056 mol) of N-methyl-N-nitroso-N'-nitroguanidine in 50% aqueous ethanol was added 7.5 g (0.06 mol) of 3-fluorobenzylamine, followed by The resulting reaction mixture was stirred for 18 hours and then 150 ml of 1N sodium trihydroxide solution were added. After filtration, the filtrate was acidified with concentrated hydrochloric acid and then filtered. 10.6 g of product are obtained in the form of a fluffy white precipitate, m.p. 177-179 ° C.

Using the procedure described above or in Scheme 1, but starting from a suitably substituted amine and 2-methyl-1- (or 3-) -nitro-2-thiopseudocarbamide, the title compound was prepared as described in Scheme II. The compounds of Formula II listed in Table II can be prepared.

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II. Compounds of formula II

w ₂ X ₂ Yi z ₂ r ₂ m Melting point (° C) F II II 11 II 0 181 183 11 sits II 11 II 0 122-125 H and ₃ H H H 0 134-136 H oc ₂ h ₅ H H H 0 125-128 H n-OC ₃ 11 ₇ H H H 0 140.5 to 141.5 H sec-OC ₄ H ₉ H H you 0 93-98 H 6-oxa-cyclohex-1-yloxy H H H 0 110.5 to 113 H ocf ₃ H H H 0 138-139 H sch ₃ H H H 0 149-152 H F H H H 0 177-179 H cl II II II 0 166 167 H Br H H 11 0 157-159 H I H H H 0 167-169 H ch ₃ H H H 0 151-153 you c ₂ h ₅ 11 II II 0 119-120.5 H cf ₃ H H H 0 164-165 H H F H H 0 205-206 H H cl H H 0 195-197 H H Br H H 0 172-174 H H ch ₃ H 11 0 181-183 cl cl H H 11 0 220-222 F CH ₃ H H H 0 198 to 198.5 F and ₃ H H H 0 162-165 cl H cl π II 0 200 202 F H F H H 0 209-211 F H H ch ₃ H 0 171.5-173 F H H F H 0 186-188 F H H and ₃ H 0 149-151 F H H H H 1 153.5-154.5 11 OCÍÍ ₃ RIP 11 11 I 88 89 H and ₃ H H H 2 122-123 H H H H ch ₃ 0 115 to 116.5 H H H H cf ₃ 0 149-151 H H II H c ₂ h ₅ 0 129.5-130.5 F H H H ch ₃ 0 99-102 H H H H ch ₃ 0 (+) - isomer 126-127 H H H H ch ₃ 0 (-) isomer 127.5 to 128 H ch ₃ H 11 ch ₃ 0 140-143 H and ₃ H H ch ₃ 0 126-130

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II. Continue Table

w ₂ X ₂ Y ₂ z ₂ r ₂ m Melting point (° C) II II F II cn. 0 133 136 cl u H H H 0 168-170 OCH ₃ H H H H 0 202-205 H CN H H H 0 206 (decomposes) H OC ₆ H _S H H H 0 145-147 H C00CH ₃ H H H 0 158,162 H CII ₂ C1I ₂ COOC ₂ I1 ₅ 11 H H 0 77-79 H OSO ₂ CH ₃ H H H 0 134-137 H H and ₃ H H 0 191.5 to 192.5 H H N (CII ₃ ) ₂ 11 H 0 211-213 H H CH ₂ N (CH ₃ ) ₂ H H 0 136-144 H H ch ₂ nh ₂ H H 0 260 H H ch ₂ ch ₂ cooc ₂ h ₅ H H 0 124-126 H H cn H H 0 166-168 and ₃ H and ₃ H H 0 200-201 H H II II C ₆ 11 ₅ 0 236-237 H F H H ch ₃ 0 135-138 H and ₃ and ₃ H H 0 152.5 to 153.5 H cl cl H H 0 208-210 II O Cll ₂ 0 11 ii 0 207.5 to 209 H and ₃ H and ₃ H 0 166-168 H ch ₃ H ch ₃ H 0 178-180 H cl H cl H 0 218-219 H H H H ch ₃ 1 178-180 H H H H ch ₂ c ₆ h ₅ 0 199.5 to 201 and ₃ H H H ch ₃ 0 188-192 Example 4 45 Π1. spreadsheet l-Cyano-3- (3,5-dichlorophenyl) guanidine Compounds of formula (UI) production 4.45 g (0.05 mol) of sodium dicyanamide in 50 ml of 1N 50 x ₃ y, Ζ ₃ Melting point (° C) to a solution of hydrochloric acid is added a solution of 8.1 g (0.05 mol) of 3,5-dichloroaniline in 50 ml of water, H H H 195-196 then that The reaction mixture thus obtained was 80- At -100 C, they are two hours. The reaction mixture is then cooled, 55 ci H H then i the precipitate was collected by filtration, washed Br H H 236-237 suk and dried when 8.75 g of from ₂ H H 234-236 m.p. 196-198 ° C. and ₃ H 11 182-184 As described above, and in Scheme K, 60 ch ₃ H H ban, but 3,5-dichloroaniline CN H H 234-235.5 instead of starting with a suitable space- tesített using an aniline derivative III. spreadsheet- cl OH H Compounds of formula (III) cl F H, 214.5-216 can be promoted. 65 cf ₃ cl H, 194-195

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II. Continue Table

X, Y ₃ z ₃ Melting point (° C) cf ₃ F H 146-148 CI1 ₃ Br II 223-225 cl ch ₃ 11 232-234 cl cl H 226-228 cl Η cl 196-198 coch ₃ II H 175-178 COOH H H N (CH ₃ ) ₂ Η H 163.5 to 164.5 cooch ₃ Η H 212-213 Η cl H H and ₃ H II NlICOCIIa II H Niche) H H OH H H COOH H H COCH ₃ H H ^ H ^ N II CH ₃ CH ₃ H ch ₃ H ch ₃ 224-227 cf ₃ H cf ₃ 263-265

Using the procedure described in Example 4 or Scheme L, but using instead of 3,5-dichloroaniline as starting material, a suitably substituted benzylamine derivative is prepared as described in Example IV. The compounds of the formula (IV) listed in Table II can be prepared.

Example 5

Cytokinin interaction study on chlorophyll biosynthesis in cucumber cotyledons

To test for cytokinin-like stimulation on cucumber plants, seeds of National Pickling cucumbers are soaked in covered plastic bowls in moist vcmiculite and exposed to green emergency lighting. The plates are then kept in the dark for 6 days at 30 ° C.

1-8 are prepared from solutions of the test compounds ^{to 15-fold} dilutions of drug concentrations of 0.0156, 0.125, 1.0, 8.0 and 64 ppm. Each solution contains 40 milliliters of potassium chloride, distilled water from a glass and up to 1.25% by volume of acetone. (The K2θ injectable compounds were originally dissolved in 100% acetone.) 10 ml of the dilution was weighed into a 10-cm petri dish, pre-filled with a layer of cellulose filter paper No. 1 from Whatman, USA. Again using light green light, we cut the cotyledons from the seedlings, taking great care to discard the related part. Eight pairs (16 dt) of cotyledons are placed in each cup with the inner (upper) cotyledons facing down. The dishes were then incubated at 30 ° C in the dark overnight (17-21 hours) and then exposed to fluorescent light at 12-14 W / n ² for 3 hours. The dishes are then stored in the dark at 20 ° C or lower, and the cotyledons are successively collected and placed in large test tubes containing 5 to 5 ml of dimethylformamide. The tubes were sealed with Parafilm and kept in the dark at 4 ° C overnight or at 30 ° C for 4 hours to extract chlorophyll.

ARC. Compounds of formula VI

w ₄ m x ₄ Y4 Z ₄ r ₂ Melting point (° C) H 0 H H H H 100-101 F 0 II 11 11 li 129-130 H 0 OCH ₃ H H 11 112-114 H 0 ch ₃ H H Η 97-98.5 H 0 F H H Η 134-136 H 0 H cl H Η 153-155 H 0 H F H Η 134-135 F 0 II H ch ₃ Η 123-124 F 0 H H and ₃ Η 129-131 H 0 H cl Η ch ₃ 171-174 H 0 II H H ch ₃ 156-158

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The extracts were analyzed at 663 nm to determine their absorbance.

The cotyledons are removed and their surface area is measured with a leaf surface meter. The results obtained with N ⁶ benzyladenine, a known cytokinin, were used to establish experimental conditions and to illustrate the cytokinin-like activity of the test compounds. Curves were plotted to determine the rate of increase in chlorophyll biosynthesis (Fig. I) and the increase in rock surface (Fig. 2). In fact, Figure 1 shows the absorbance at 663 nm. In this series of experiments, 1-nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine is tested among the compounds of the invention. Comparing with each other the two eredménygörbét, so that N results obtained with ^6-benzyl adenine (a "Standard Cytokinin" nel) a compound of the invention obtained above. Figure 1 shows the rate of chlorophyll formation and Figure 2 shows the increase in cotyledons. The experimental methods used here are similar to those described by Elcteher et al., Plant Pltysiology, 6'Z 675 677 (1982), and Morán and Porath, Plant Physiology (1980).

The dose-response curves shown in Figures 1 and 2 clearly demonstrate that both N ⁶ benzyladenine and 1-nitro-3- (3-trifluoroethyl-4-fluorophenyl) guanidine are active compounds in this biological. test method.

In Figures 1 and 2 of the curve), the resulting curve F ^{6-benzyl-adenine,} whereas curve b) is the curve obtained with the present compound.

Further compounds of the invention were tested by the assay method described above. In the following, these compounds are described in p. p. m. units required to achieve 50% of the maximum effect.

Test compound E » _s ' (p Mon - m) l-Nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine 0.48 l- (3-methoxy-benzyl) -3-nitro- guanidine 1.8 l- (3,5-dichloro-phenyl) -3-nitro- guanidine 0,125 1-Nitro-3- (3-trifluoromethyl-phenyl-guanidine) 0,125 1-Cyano-3- (3-trifluoromethylphenyl) guanidine 0.22 l-Nitro-3-phenyl-guanidine 8.0 l-Benzyl-3-nitroguanidine 5.7

Experimental compound! l ', ₀ {p. 1- (3-Chloro-benzyl) -3-nitro-guanidine 3.8 l-Cyano-3- (3-trifluoromethyl-phenyl) - guanidine 2.5 l- (3-Methoxy-fenir) -3-nitroguanidine 1.0 l- (3-iodo-phenyl) -3-nitroguanidine 0,125 l- (3-Bromophenyl) -3-nitroguanidine 0.48 l- (3-Bromophenyl) -3-cyanoguanidine 1.0 l- (3-Chlorophenyl) -3-nitroguanidine 1.8 1- (3-Chloro-phenyl) -3-cyano-guanidine 1.8 l- (3-FLUOROPYRIDIN-phenyl) -3-nitro-guatiidin 8.0 1-Ni Thio-3- (3-methylpentyl) guanidine 1.0 1-Cyano-3- (3-methylphenyl) guanidine 1.0 1-Cyano-3- (3-trifluoromethylenenyl) - guanidine 0.22 l- (3-Methoxyphenyl) -3-nitroguanidine 1.0 1- (3-Difluoro-methoxy) -phenyl-3-nitroguanidine 0.06 1-Nitro-3- (3-trifluoromethoxyphenyl) gunnidine 3.8 l- (3-Methyl-thio) -3-nitroguanidine 1.0 l- (3-Ethoxy-phenyl) -3-nitroguanidine 3.8 1-Nitro-3- [3- (1,2,2,2-tetrafluoroethoxy) phenyl] guanidine 0.48 l - (. 3-hydroxymethyl-phenyl) -3-nitro- guanidine 2.5 1- (3-Mcoxymethylphenyl) -3-nitroguanidine 1.8 1-Nitro-3- [3- (2,2,2-trifluoro-1,1-dihydroxyethyl) phenyl] -guanidine 0.48 3- (3-Nitro-guanidine) benzoic acid methyl ester 3.8 ) - (3-acetylphenyl> 3-nitroguanidine 3.8 l- (3-cyanophenyl) -3-nitroguanidine 1.0 l- (3-cyanophenyl) -3-cyanoguanidine 8.0

-1223 195 637 24

Test compound i n, ₀ tp. p. tendon.) Experimental blend II), "(p. In.) l- (3-Cyano-methyl-phenyl) -3-nitro- 1- (2-Fluorobenzyl) -3-nitroguanidine 3.8 guanidine 3.8 5 1- (3-iodobenzyl) -3-nitroguanidine 14.0 l- (3-Nitrophenyl) -3-nitroguanidine 8.0 l- (3-Chloro-benzyl) -3-nitroguanidine 3.8 l- (3-Dimethylamino-phenyl) -3-nitro- guanidine 3.8 10 1- (3-Bromobenzyl) -3-nitroguanidine 5.7 l-Cyano-3- (3-methoxyphenyl) guanidine 2.5 l- (3-fluorobenzyl) -3-nitroguanidine 8.0 l- (3-Chloro-4-fluoro-phenyl) -3-nitro- 15 l- (3-methylbenzyl) -3-nitroguanidine 8.0 guanidine 1.8 l-Cyano-3- (3-methyl-benzyl) guanidine 8.0 l- (3-Chloro-4-fluorophenyl) -3-cyano- guanidine 14.0 1-Nitro-3- (3-trifluoromethylbenzyl) - 20 guanidine 8.0 l- (3,4-Dichlorophenyl) -3-nitroguanidine 1.0 l- (3-Methoxybenzyl) -3-nitroguanidine 1.8 l- (4-bromo-3-methyl-phenyl) -3-nitro- guanidine 1.0 l-Cyano-3- (3-methoxybenzyl) guanidine 2.5 25 1- (4-Chloro-3-methyl-phenyl) -3-nitro- l- (3-Ilidroxi-benzyl) -3-nitrobenzoic guanidine 1.0

guanidine 1,8 1- (3-Phoxybenzite) -3-nitroguanidine 8.0 1- (4-Fluoro-3-methylphenyl) -3-nitroguanidine 3.8

30 l-Nitro-3- (3-propoxy-benzyl) guanidine 1.3 1-Neuro-3- (3,4-xylyl) guanidine 3.8 l- (3-57.ck-Butoxy-benzyl) -3-nitro- l- (4-Chloro-3-trifluoromethyl-nietiI-phenyl) -3-nitro- guanidine 0.31 guanidine 1.0 35 8.0 1- (4-FI u -Benzyl) -3-nitroguanidine 1- (3,5-Dib-Romophenyl) -3-nitroguanidine 0,125 l Nií.o-3- / 3- (tetrahydro-2H-pyran-2-yl l- (3,5-Dichlorophenyl) -3-nitroguanidine 0,125 benzene) / guanidine 1.0 1- (3,5-Dichlorophenyl) -1-methyl-3-nitro- 40 l- (2 '> -. difluorobenzyl) -3-nitroguanidine 5.7 guanidine 3.8 l- (2-Fluoro-5-methoxycarbonyl-benzyl) -3-nitro- 1-Cyano-3- (3,5-dichlorophenyl) guanidine 0.48 guanidine 2.5 l- (3,5-Dimethoxyphenyl) -3-nitroguanidine 14.0 45 1- (2-Fluoro-5-methyl-benzyl) -3-nitroguanidine 8.0 l- (5-bromo-3-methyl-phenyl) -3-nitro- guanidine 0.48 1- (2,4-Difluorobenzyl) -3-nitroguanidine 10.6 1-Nitro-3- (3,5-xylyl) guanidine 3.8 50 1- (2,4-Dichlorobenzyl) 3-nitroguanidine 8.0 l- / 3,5-di (trifluoromethyl) phenyl / -3 1- (alpha-methyl-benzyl) -3-nitro-guanidine 1.8 nitroguanidine 3.8 55 l- (3-methoxy-phenethyl) -3-nitroguanidine 14.0 1- (2-Fluoro-3-methoxybenzyl) -3-nitroguanidine 2.5 l-Nitro-3- / a- (trifluoromethyl) benzyl / - guanidine 2.5 1-Ni tro-3- (3,4,5-trichloro-phenyl) guanidine 3.8 60 l- (alpha-ethyl-benzyl) -3-nitroguanidine 0.22

1- (4-Chloro-3-trifluoromethyl-phenyl) -3-cyano-guanidine 2.5

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Example 6

Investigation of the mechanism of action of cytokinin-like activity in tissue culture

Cytokinins are involved in and influence plant cell division. The cytokinin-like activity of an unknown compound is considered to be proven if it is capable of replacing a known cytokinin in such a way that a cytokinin-dependent cell culture can grow in the presence of a particular medium. Calli cultures from acme soybean cotyledon need a cytokinin to grow on agar agar medium. These callus cultures are used in this assay to determine whether the compounds of the present invention promote cell division.

Callus is prepared by secondary culturing in a medium containing vitamins, mineral salts, 3% sucrose, 0.9% agar and 2 ppm naphthalene acetic acid (PNAS, 54, 1052-1058 (1965)). Ali requires the addition of 10 to ⁷ moles of N ⁶ benzyl adenine under normal conditions to increase callus. The experimental media are thus prepared by omitting the known cytokinin, i.e. N ⁶ -benzyladenine, and in varying concentrations by the compounds of interest. Plastic petri dishes (15 mm to 60 mm) are poured into 6-6 ml of agar-agar medium containing the test compounds. The callus is scraped off the secondary culture plates, carefully broken into small pieces and mixed with agar agar diluted with the basic medium. Subsequently, 2 to 2 ml of the mixture thus obtained are layered on each experimental medium. The dishes are kept in the dark at 25 ° C for 8 days and then examined for growth of callus on various experimental media. The results are shown in Table V.

Table V.

Stimulation of growth of cytokinin-dependent tissue culture on a given medium

Table V. Continue concentration increasing Test compound ration (p. p. m.) callus percentage ³ ) l- (3-Methoxy-benzyl) -3- 3.0 15.0 nitroguanidine 10.0 30.0 100.0 100.0 100.0 100.0 N ⁶ benzyl adenine 10 ⁷ M. 100.0

a) - Growth is examined visually by comparing small brown cell nodules (no growth) with those that are large and white (there is growth)

The results of Table V show that the compounds of the present invention are capable of replacing N ⁶ benzyl adenine, i.e. having cytokinin-like activity.

Example 7

Aging tests on leaf cut leaf discs

Leaf discs are made from locally purchased Romainc lettuce, and 4-4 discs per treatment are placed in Petri dishes containing Whatman No. 1 filter paper and 10 µl of the test compound. p. m (0.2% acetone) or 100 p. p. (2% acetone). The plates were stored in the dark at room temperature for 5 days and then the disks were extracted with dimethylformamide and the chlorophyll absorbance was measured at 663 nm. Table.

VI. spreadsheet

Investigation of the anti-aging effect of test compounds on lettuce leaf discs

Test compound Concentration (P-P · ni.) Percentage of increasing callus ³ ' ¹ Untreated control She 0.3 l- (3,5-Dichlorophenyl) -3- 0.1 4.0 nitroguanidine 0.3 100.0 1.0 100.0 1-Nitro-3- (3-trifluoro- 0.3 8.0 methyl-4-fluorophenyl) - 1.0 100.0 guanidine 3.0 100.0 10.0 100.0

Λ ktorolyl-

Ghostly compound Concentration (p. M) % increase in retention relative to untreated control 3-Trifluoromethyl-phenyl dicyandiamide 100 18 1-Benzyl-3-nitroguanidine 10 18 l-Nitro-3- (3-trifluoromethyl-nictil- phenyl) guanidine 100 16

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VI. Continue Table

Chlorophyll-

Test compound Concept l- rationality (p. 111.) nicoglobulin increase in% compared to untreated control 1- (3,5-Dichloro-phenyl) -3-nitro-guanidine 10 14 l-Nitro-3- (3-trifluoromethyl 4-fluoro-phenyl) -guanidine 10 40 l- (3-Methoxy-benzyl) -3-nitro- 10 11 guanidine 100 15 1 -Cyano-3- (3-trifluoromethyl) 10 33 4-fluorophenyl) guanidine 100 17 1- (3-Methoxyphenyl) -3-nitro- 10 17 guanidine 100 34 1-Cyano-3- (3-Me Toxybenzyl) - 10 40 guanidine 100 26 l-Nitro-3- (3-trifluoromethyl benzyl) guanidine ¹⁰ 26 l-Nitro-3-phenyl-guanidine 10 10

From the data in the table it can be seen that the chlorophyll retention on lettuce discs treated with the compound of the invention is about 10-40% higher than in the untreated control.

Example 8

Lima bean leaf discs increase in size

In this experiment, it has been found that bean leaf discs respond to treatment with an aqueous solution of various compounds of the invention by increasing their size. Place 5 to 6 of the 2.2 cm ² leaf discs in 15 · 100 mm Petri dishes containing three layers of Whatman filter paper No. 1 and 12 ml of 40 mM potassium chloride solution (dissolved in this solution). test compound in various concentrations). The dishes were exposed for 6 days and the surface was measured with an area meter. Many test compounds have the ability to increase the area growth of discs. The results obtained are shown in Table VII. are summarized in Table.

VII. spreadsheet

Increased leaf crowns of Lima beans

Test compound Concentration (p. P. M.) % Increase of leaf diskcriilct ' control 0 34 1- (3-Methoxyphenyl) -3- 0.12 87 nitroguanidine 1.0 103 l-Nitro-3- (3-trifluoro 1.0 92 me til-4 flu or -methyl) - 8.0 107 guanidine

-9. example

Investigation of the growth-promoting effect of the compounds of the invention on radish seedlings in liquid media

In these experiments, Cherry Bcllc seeds, sterilized on their surface, were aseptically placed in 125 ml Erlenmeyer flasks containing 20 to 20 ml of autoclaved medium. The medium contains distilled water as well as mineral salts used in plant cell cultures such as 300 mg / L potassium dihydrogen phosphate, 65 mg / L potassium chloride, 4.9 mg / L manganese sulfate monohydrate,

2.7 mg / l of zinc sulphate heptahydrate,

1.8 mg / l boric acid, 0.35 mg / l ^40% copper (II) sulfate pentahydrate, 0.1 mg / l ammonium molybdenate tetrahydrate [(ΝΗ ₄ ) _ύ Μο ₇ Ο ₂₄ · 4 HiO, 499 mg / l calcium nitrate tetrahydrate, 1 g / l potassium nitrate, 1 g / l ammonium nitrate, 71 mg / l magnesium sulfate heptahydrate and 42 mg / l commercially available % iron chelate plus the test compound at appropriate dilution (the latter being 5000 ppm of the technical grade test compound

Diluted from acetone stock containing 5 °). Prior to autoclave heat treatment, the pH of the medium is adjusted to 5.8, and then the test compound is autoclaved immediately following the flask! Add 10 to 20 seeds before adding to the medium. The dishes were kept on a rotating shaker at room temperature under dim fluorescent light for 6 days. The seedlings are then removed, the moisture absorbed ₆₀ and the various parts cut off, then their fresh weight is measured and / or the chlorophyll content is determined.

The results obtained by Vili. are summarized in Table.

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Vili. spreadsheet

Compounds of the Invention Growth Promoting Effects on Radishes 5

Test compound Concentration (p. P. M.) Percentage increase in fresh weight of reticulum rock compared to untreated control Untreated control 0 - l- (3,5-dichlorophenyl) - 0,001 -4 nitroguanidine 0,003 -4 0.01 +24 0.03 +64 0.1 +92 0.3 + 151

It is seen that radish cotyledons show a _{20 to} 150% increase in weight compared to untreated control when said cotyledons are treated with 0.01 to 0.5 ppm of 1- (3,5-dichlorophenyl) 3-nitroguanidine. .

Example 10

Superior potato tubers (Solanum tuberosum) 35 early stimulant effect

In greenhouse experiments, when exposed to the compounds of the invention 40 by hydroponic treatment for 48 hours, the roots of young potato seedlings produce larger tubers in the early stages of germination than untreated controls. This suggests that, under field conditions, the treated plants may produce more tubers up to size. size 1 as required by the United States Standard.

Thus, in the experiments, potato seedlings of the Superior variety were grown on vermiculite until they were 7 cm high. The seedlings are then treated with various concentrations of the compounds of the invention in aquatic culture for 48 hours and then seeded in a greenhouse for 2 months prior to evaluation. 4-4 plants per treatment are used. The higher number of tubers over 62 g in the plants treated with the test compounds demonstrates the effect on early tuber development. In the untreated female plants, 20% of the tubers fall into this weight group, while in the treated plants 29-81%. In the long run, tubers weighing more than 62g are expected to reach 40-60% of their expected final weight, i.e. they will meet size 1 according to the said standard.

The results obtained are shown in Table IX. Table.

Example 11

Effect on inhibition of rice sprouting in the case of stubble cultivation

In this experiment, rice seedlings of IR-36 varieties suitable for flood rice production are planted in 12 m ² plots in quadruplicate, planting 3 to 3 seedlings per lay. Landfill sizes are 25 · 25 cm. The soil is then 60 with respect to nitrogen

IX. spreadsheet

Size increase in early-stage tubers of superior variety potatoes

Test compound Concentration (p.p.m.) Total weight (g) % increase over untreated controls Percentage of the total weight of tubers Untreated control 0 77 0 20 1- (3,5-Dichlorophenyl) -3-nitro- 0.1 175 127 52 guanidine 1.0 240 217 57 l-Nitro-3- (3-trifluoromethyl 0.1 102 32 29 phenyl-guanidine 1.0 140 82 41 10.0 419 184 81 1- (3-Methoxybenzyl) -3-nitro- 1.0 107 39 32 guanidine 10.0 108 40 29 100.0 182 136 64

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195 637 kg / ha, 30 kg / ha of phosphorus and 40 kg / ha of potassium are fertilized. Plots are sprayed with a 20:80 (v / v) water / acetone mixture of the test compound and 0.25% nonionic wetting agent (i. , and 30 kg / ha of nitrogen and 30 kg / ha of additional fertilizer treatments are applied 30 days after spraying. Treatment with the test compound is, moreover, carried out at the stage of the development of the garland inflorescence (corresponding to the so-called Zadok condition Z 31/32). The evaluations are performed in an area where the forces causing the tilt are usually strong. During the growing period, the water level in the plots is maintained at about 3-5 cm. Four months after planting, the parcels are inspected and the rice is harvested from an area of 6 m ² . The results obtained are given below.

Experimental Concentration Percent compound (Kg / ha) lurch Untreated control 0 100 1- (3,5-Dichlorophenyl) -3- 1 20 nitroguanidine 2 10 4 5

i

Example 12

Impact on yield increase in case of rice production under price

The experimental procedure of Example 11 was repeated, except that the aqueous-acetone mixture of the test compound was applied to the planted rice IR-36 when the plants reached their maximum bush condition and the test compound and the non-ionic A solution of a humectant in a mixture of 20% water and 80% acetone is applied to the already bushy rice in such quantities that it is equivalent to 11, 33 or 100 g of test compound per hectare. About four months after planting, the rice is harvested. The results obtained are given below.

Example 13

Impact on the increase of seed yield in the case of wheat and barley

It establishes, surprisingly, that the compounds of the present invention ²⁰ are effective in inducing early maturation of grains such as wheat and barley.

In the May ash week, part of the soil is pre-plowed with Sindton spring wheat (2.44 ²⁵ hectoliters / hectare), which is pre-plowed with 896 kg / ha of so-called 9: 9: fertilizer. Another part is planted with 2.09 hectoliters / week of spring barley of the Herta variety. Each area is divided into 12 m ² plots. When the plants reach the so-called Zodak 30/31 condition, the plots are sprayed with 20 volumes of the test compound in 80 volumes of acetone; water containing 0.25% nonionic wetting agent, ₃₅ wt.%, 9 mol. of ethylene oxide, a wetting agent consisting of nonylphenol, oleic acid and isopropanol. The test compound is applied in an amount such that the application rate per hectare corresponds to 0 (untreated control) and 0.22, 0.67 and 2.0 kg, respectively. Each treatment is performed five times. Harvesting is carried out 7 weeks after sowing. The moisture content of the harvested grain is adjusted to 15% and the weight is then weighed. The results obtained are reported in Table X. Fever.

Rice yield increase

. . 1 Rate of use Yield * For control Test compound (G / ha) (T / ha) compared to% yield Untreated control - 4.46 100 1-Potassium-3- (3,5-dichlorophenyl) -1-nitroguanidine 11 5.21 117 33 4.70 105 100 4.58 103

+ = 14% humidity

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Table X.

Investigation of the effect of increasing wheat and barley yields

Test compound cereals Rate of use grain Yield control (Kg / ha) hectoliters / hectare %-the 1- (3,5-L-cyclohexyl) - spring 0 (control) 25.84 3-nitroguanidine wheat 0.22 29.84 115 0.67 30.80 119 2.0 29,32 113 1- (3,5-Dichlorophenyl) - spring 0 (control) 22.62 2-methyl-3-nitro- wheat 0.22 25.14 111 guanidine 0.67 26.19 116 2.0 24.80 110 1- (3,5-Dichlorophenyl) - spring 0 (control) 30,10 3-nitroguanidine barley 0.22 32.90 108 0.67 33.20 109 2.0 34.80 114

Example 14

Effect on the increase in yield of cotton (Gossypiurtí hirsutum cv Acala)

In this experiment, the 35 crops mentioned in the title are sown in the third week of April on pre-plowed, harrowed and fertilized areas. Sowing is carried out with an average of 12 plants per row and approximately one meter apart. Each parcel is four meters long. Two treatment repeats are used. 40 Four weeks after sowing, when the cotton plants reach a state of two to three leaves, the plants are sprayed with a mixture of 50 volumes of water containing, on the one hand, 0.25% non-ionic, phthalic and glycerol-based silk resin. 45 tat as an emulsifier and spreading agent, and sufficient amounts of the test compound to provide a treatment rate of 0.0 (untreated control), 0.062, 0.125 or 0.25 kg of active ingredient per hectare. About 50 weeks after sowing, when the cotton plants reach the first flowering stage, different and untreated plots of the same area are sprayed with solutions of the test compounds prepared as above. All plants are then allowed to grow to $ 5 maturity using standard cultivation methods. During the second week of October, the cotton is harvested by hand on each parcel and weighed. The results obtained for each treatment are shown in Table XI. The average weight harvested per hectare in ⁶⁰ replicates for each treatment is given in Tables 3 to 5.

XI. Yield-lowering effect of l-nitro-3- (3-trifluoromethyl-4-fluorophenyl) glycanide on cotton

Application time'- group gives Application gold (Kp / IIa) Average weight of cotton seed (kg / parcel) 2-3 leaves 0.0 (control!) 0.062 1.57 1.72 2-3 leaves 0.0 (control) 0.125 1.70 1.85 2 3 leaves 0.0 (control) 0.25 1.97 2.22 First flowering 0.0 (control) 0.062 1.73 2.25 First flowering 0.0 (control) 0.125 1.61 2.20 First flowering 0.0 (control) 0.25 1.85 2.45

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195 637/5. example

Effect on increasing the number of American standard size I potatoes and increasing the total weight of potato tubers produced per plant

During these trials, in the first week of April 2016, Superior potato (Solanum tuberosum) was planted at a rate of 2016 kg / ha. About 5 weeks after planting, when more than 50% of the potato plants have hatched, plots of 0.9 meters apart containing two 9.6 meters long rows are sprayed with 50 volumes of acetone and 50 volumes of water. containing 0.25% by weight of modified phthalic acid and glycerol-based alkyl gels as a filtering agent and spreading agent, and sufficient amounts of test compound to provide 0.0 per hectare (untreated control),

Apply a treatment of 0.25, 0.50 or 1 kg of active ingredient. 6 repetitions are used per treatment. Additional plots are sprayed at similar intervals and at weekly intervals.

The treated plants are then treated by standard cultivation methods. When the plants reach maturity, we harvest about 20 weeks after sowing. The number of potatoes of standard size 1 and the total weight of potatoes are determined per plot. The results obtained are shown in Table XII. and XIII. tables.

XII. spreadsheet

Increase in number of potato tubers of size 1 per plant (Solanum tuberosum SuperiorJ

Test compound Application gold (Kg / ha) Percentage of size 1 tubers away control Ε2 E3 l-nitro-3- (3-trifluoromethyl-4-fluorophenyl) - 1.0 +21 +27 + 15 guanidine 0.50 + 23 +28 + 14 0.25 +21 +30 + 19 1- (3-Chloro-4-fluorophenyl) -3-nitroguanidine 1.0 + 19 + 24 + 19 0.50 + 25 + 20 + 7 0.25 +21 + 24 + 14 l- (3-Methoxybenzyl) -3-nitroguanidine 1.0 + 10 + 36 + 19 0.50 + 18 + 32 +20 0.25 + 23 + 34 + 18 l- (3,5-dichlorophenyl) -3-nitro-guanidinopropyl 1.0 + 12 + 38 + 13 0.50 + 14 + 35 +8 0.25 + 15 +34 + 10 E1, E2, E3 = use of test chemical a hatching of potato seedlings 1.2 or 3 weeks after XHI. spreadsheet Increase in total potato weight compared to control, yielding 42.6 tonnes / ha Application Potatoes per treatment! total weight Test compound gold compared to the control (Kg / ha) away E2 E3 l-Nitro-3- (3-trifluoromethyl-4-fluorophenyl) - 1.0 + 17 + 23 + 13 guanidine 0.50 + 19 +24 + 12 0.25 + 18 + 26 + 16 1- (3-Chloro-4-fluoro-phenyl) -3-nitro-guanidine 1.0 + 15 +20 + 17 0.50 +21 + 16 + 5 0.25 + 18 + 20 + 11

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XIII. Continue Table

Test compound Application gold (Kg / ha) Potatoes per treatment! total weight relative to control away E2 E3 l- (3-Methoxybenzyl) -3-nitroguanidine 1.0 +7 + 25 + 16 0.50 + 15 + 38 + 17 0.25 + 20 + 30 + 14 1- (3,5-Dichlorophenyl) -3-nitroguanidine 1.0 + 11 + 32 + 11 0.50 + 12 +30 + 6 0.25 + 9 +28 + 7

E1, E2, E3 = Application of the test compound 1.2 or 3 weeks after hatching of the potato seedling

Example 16

Effect on the increase in the total weight of the potatoes

The procedure described in Example 15 was followed except that a wide variety of compounds were used as test compounds. The test compounds are applied at a rate of application of 0.25 to 2.0 kg / ha two weeks after seedling emergence. We harvest the potatoes 20 weeks after sowing. The data obtained are shown in Table XIV. Table I is a table comparing the total fresh weight of the potatoes with the total fresh weight of the untreated control plots. The experiments were repeated, except that the test compounds were used in the form of a 30% liquid formulation which was dispersed in water prior to use and then applied as an aqueous pennet. The results obtained are described in XIVa. Table.

The liquid concentrates used in the latter experiments have the following composition:

% By weight

Component quantity

Test compound (90% purity) 30.00 Colloidal magnesium aluminum silicate 0.40 Sodium salts of polymerized alkylnaphthalenesulfonic acids 1.50 Propylene glycol / Dipropylene glycol 8.00 Ethoxylated octylphenol 0.10 nonyl-phenoxy-polyethoxy-ethanol 0.10 citric acid 0.07

xanthan gum 0.06 paraformaldehyde 0.10 esapvíz 59.67

100.00

XIV. spreadsheet

Increase in total potato weight

45 Experimental vcgyiili Application gold (Kg / ha) Total fresh weight of tubers compared to untreated flax control 50 Untreated control - 151 cwt / A l-Benzyl-3-nitro- 2.0 + 12 guanidine 0.5 + 13 55 1-Nitro-3- (3-trifluoromethyl-phenyl) -guanidine 0.5 +9 1- (3-Acetylphenyl) -3- 1.0 + 18 nitroguanidine 0.25 +6 60 1- (3-Methoxyphenethyl) - 2.0 +5 3-nitroguanidine 0.5 + 10 65 l- (4-Chloro-3-methyl- phenyl) -3-nitroguanidine 0.5 +4

-2 040

XIV. Continue Table

Experimental blend consumption gold (Kg / ha) Total fresh weight of tubers compared to untreated control l- (3-Methoxy-phenyl) -3- nitroguanidine 0.5 +3 l- (3-Fluoro-benzyl) -3- nitroguanidine 2.0 +6 1- (3-Bronophenyl) -3- 2.0 +2 nitroguanidine 0.5 + 17 l-Nitro-3- (3,4-xylyl) - guanidine 0.5 +3 l- (3-difluoromethoxy 2.0 +2 phenyl) -3-nitroguanidine 0.5 +20 l-Nitro-3- (3-píopoxi- benzyl) guanidine 2.0 + 25 1- (alpha-methylbenzyl) - 2.0 +9 3-nitroguanidine 0.5 + 16

⁺ cwt / A = 100 lbs / 4046 m ²

XIVa. spreadsheet

Increase in total potato weight with liquid concen trate containing 7 test compounds

Total fresh weight of tubers

Test compound gold (Kg / ha) compared to untreated controls l-Nitro-3- (3-trifluoro 0.5 + 11 methyl-phenyl-guanidine 0.25 + 11 0,125 + 11 1- (3,5-Dichlorophenyl) - 0.5 +8 3-nitroguanidine 0.25 +8 0,125 + 11 1-Nitro-3- (3-trifluoro- 0.5 +8 methyl-4-fluorophenyl) - 0.25 +8 guanidine 0,125 +4 l- (3-Methoxybenzyl) 0.5 +6 3-nitroguanidine 0.25 + 13 0,125 +5

For untreated controls, the average total yield is 202 lbs / 4046 m ² .

Example 17

Effect on the increase in weight of potatoes of the Kennebec variety

The procedure of Example 15 was repeated, except that Kennebec potatoes were used in the experiments. The test compounds were applied as a solution in the form mentioned in Example 15 on a mixture of steel and water at a rate of application of 0.5 to 2.0 kg / ha. The potatoes are harvested after ripening, about 20 weeks after sowing. The results obtained are shown in Table XV. Table. Results are expressed as the ratio of the total fresh weight of the potato to the total fresh weight of the untreated control potato.

XV. spreadsheet

Increasing the total weight of Kennebec potatoes

Total fresh weight of tubers

Ratio of test compound to untreated (kg / lut) control

1 -Cinano 3- (3-trifluoro- 2.0 + 14 methylphenyl) guanidine 0.5 +7 l-Benzyl-3-cyano guanidine 0.5 + 16 1- (3-Cl Cl-Phenyl) -3-nitroguanidine 2.0 +9 l-Nitro-3- (3,5-xylyl) - guanidine 2.0 +9 1- (3-Methoxybenzyl) -3- 2.0 +15 nitroguanidine 0.5 +6 l- (3-Methyl-benzyl) -3- nitroguanidine 2.0 +6 l-Cyano-3- (3-Methoxy- beuzilj-guanidis! 2.0 +5 l- (4-Fluoro-benzyl) -3- 2.0 +8 nitroguanidine 0.5 +4

Example 18

Increasing the number and total weight of potato tubers corresponding to size 1 for different potato varieties

The procedure described in Example 15 is followed, but with the following differences:

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195,637 after application of burgol yap palates from the soil.

The varieties used in the studies are Katahdin,

They were Kennebec, Norchip and Superior.

The results obtained are shown in Table XVI. Table.

(1) Λ test compounds are applied at rates of application of 0.25 kg / ha or 1.0 kg / l.

(2) Various varieties of potato (Solanum tuberosum) are utilized.

(3) Test compounds for one to two weeks

XVI. spreadsheet

Increase in the number and total weight of potato tubers # 1

ΚΛΤΛΙΐηΐΝ-Leitha

Experimental Application Fresh Weight of Tubers Compared to Untreated Control Compound Ratio (kg / ha) El E2

Size 1 tuber Osc. Size 1 tuber

l-Nitro-3-trifluoro-methylpyridin-4- 1.0 + 13 + 14 + 12 + 15 methyl-4-fluorophenyl) guanidine 0.25 + 13 + 12 + 15 + 18 1- (3-Methoxybenzyl) -3- 1.0 + 21 + 21 + 11 + 13 nitroguanidine 0.25 + 18 + 18 +4 + 6

Average yield of untreated control: 207 inas / 4046 ni ^{2 out} of size ¹ total 232 mesas / 4046 tn ²

El = Test compound applied 1 week after seedling emergence E2 = Test compound applied 2 weeks after seedling emergence

Experimental chemical compound Application rate (kg / ha) Kennebec-kind Total fresh weight of tubers compared to untreated control E2 Sum. away Size 1 tuber t. size tuber Sum. 1-Nitro-3-β-trifluoro 1.0 -11 -8 + 16 + 17 methyl-4-fluorophenyl) guanidine 0.25 + 6 + 5 + 9 + 10 1- (3-methoxybenzyl) _; - 1.0 -3 -2 +3 +4 3-nitroguanidine 0.25 0 +1 +4 + 6

Average yield of untreated control: 1, 257 lbs / 4046 m ^{2 of} total size 307 lbs / 4046 m ²

Experimental Latvia compound Application rate (kg / ha) Total fresh weight of tubers Size 1 tuber NORCHIP-kind compared to untreated controls Sum. i Sum. 1 Γ . size tuber 1 -Nitro-3 (3-trifluoro- 1.0 +12 + 11 +1 +4 methyl-4-fluorophenyl) guanidine 0.25 +7 +7 + 7 + 7 1- (3-Methoxybenzyl) - 1.0 +7 + 7 + 3 +5 3-nitroguanidine 0.25 + 10 + 10 +4 + 3

Average yield of untreated control: Size ¹ 302 lb / 4046 m ² total 368 lb / 4046 m ²

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XVI. Continue Table

Experimental compound l'heat rate (kg / ha) SLH'ERIOR-Iajta Tubers Fresh fall fescue compared to untreated till roll 2 Sum. K No. 1 tuber 1 Sum. 1 Size 1 tuber l-Nitro-3- (3-trifluoro 1.0 + 16 + 14 + 19 + 19 methyl-4-fluorophenyl) - 0.25 + 14 + 14 + 22 + 21 guanidine 1- (3-Methoxybenzyl) -3- 1.0 + 14 + 13 + 16 + 14 3-nitroguanidine 0.25 + 17 + 15 + 27 +22

Average yield of untreated control: 283 mesh / 4046 m ^{1 from} size ^1, 322 mesh / 4046 m ²

Average untreated control yield: 398 lbs / 4046 m ² 1- (3-Cl Cl-Phenyl) - 1.0 410 3-nitroguanidine 0.5 +6 0.25 43 0,125 +7 Average untreated control 392 lbs / 4046 m ² 1 (4-Chloro-3-trifluoro- 1.0 + 10 methyl-phenyl) -3-nitro- 0.5 +5 guanidine 0.25 +8

0.125 +4

The average total yield for untreated control was 391 m 2/4046 m ²

l- (4-Bromo-phenyl 3rmetil ·) - 1.0 +2 3-nitroguanidine 0.5 +4 0.25 +4 0,125 +6

Average untreated control yield: 410 lbs / 4046 m ²

1 (3-Chloro-4-fluorophenyl) - 1.0 +8 3-nitro-guaiudin 0.5 '+6 0.25 +5 0,125 0

In untreated controls, the average total yield is 412 lbs / 4046 m ²

Example 20

Increasing the total weight of the Superior variety and the number of tubers corresponding to size 1

The procedure described in Example 15 was followed, except that the test compounds were applied at a rate of application of 0.0625 kg / ha to 1.0 kg / son two weeks after sowing, two weeks ₅₅ before emergence or three weeks after emergence. after hatching. The test compounds were used as solutions containing 0.25% nonionic surfactant in 50% acetone / 50% water. The potatoes are harvested after ripening, i.e. about 20 weeks after sowing.

The results obtained in the XVIII. table.

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XVIII. spreadsheet

Increase in the number and total weight of size 1 potato tubers

Tubers are fresh whole weight untreated

Test compound Application gold control 1. sled tuber Sum. l- (3,5-Dichlorophenyl) -3-nitroguanidine 1.0 + 13 + 14 0.5 +7 +8 0.25 +4 +7 Average yield for untreated control: 0,125 +1 +3 glaze / 4046 m ^{2 to} size 1, mass / 4046 m ² total 0.0625 +9 + 11 l-Nitro-3- (3-trifluoromethyl-rnetil4-fluorophenyl) guanidine 1.0 + 13 + 14 0.5 +5 +4 0.25 +1 +1 Average yield for untreated control: 0,125 +2 +4 glaze / 4046 m ^{2 to} size 1, mass / 4046 m ² total 0.0625 +5 +5 l- (3-methoxy-benzyl]) - 3-nitroguanidine 1.0 + 10 + 11 0.5 +6 +6 0.25 +4 +5 Average yield for untreated control: 0,125 +4 +5 grease / 4046 m ^{2 to} size 1. glaze / 4046 in ² total 0.0625 +4 +5 1- (3,5-Dichlorophenyl) -3-nitroguanidine 1.0 + 11 +7 0.5 + 19 + 18 0.25 + 10 + 12 Average yield for untreated control: 0,125 + 12 + 10 glaze / 4046 m ^{2 to} size 1, mass / 4046 m ² total 0.0625 + 19 + 18 l-Nitro-3- (3-trifluoromethyl-phenyl-4-fluorophenyl) guanidine 1.0 + 16 + 12 0.5 + 17 + 17 0.25 + 11 + 12 Average yield for untreated control: 0,125 +4 +4 glaze / 4046 m ^{2 to} size 1, mass / 4046 ni ² total 0.0625 + 14 + 13 1- (3-Methoxybenzyl) -3-nitroguanidine 1.0 +5 +3 0.5 + 10 +3 0.25 +8 +9 Average yield for untreated control: 0,125 +9 +8 glaze / 4046 in ^{2 to} size 1, mass / 4046 m ² total 0.0625 +7 +7

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Example 21

Increasing the total fresh weight and the number of tubers corresponding to size 1 in the case of Superior potatoes by the use of experimental compounds in the form of an emulsifiable concentrate or aqueous dispersion

In this series of experiments, Superior-type potatoes are sown in mid-April, and three weeks after emergence, plots of two 9.6-meter rows are sprayed with an aqueous dispersion of one of the three formulations described below.

Preparation 1

component Weight% quantity l- (3,5-dichlorophenyl) -3-nitro guanidine 11.0 N-methylpyrrolidone 38.0 Tenneco 500/100 aromatic solvent * ^ 35.0 T-Mulz 339 Emulsifier ^xx) 6.0 Multifilm X-77 Spreading Agent ^xxx ) 10.0 100.0

(x) Tenneco 500/100 aromatic solvent is manufactured by the US company Tenneco Oil Company (Houston, Texas) and has the following characteristics:

specific gravity 15.56 / 15.56 ° C 0.860-0.875 acidity no flash point (TTC min), ° C 37.8

Kouri-Butanol value, min 92 minimum aromatic content, volume '/? 95 distillation temperature above 143 ° C (xx) T-Mulz 339 emulsifier is a product of Thompson Hayward Chemical Company (Kansas City, Kansas) and a mixture of anionic non-ionic emulsifying surfactants xxx) Multifilin X-77 a Coiloidal Products Corporation (Sausalito, CA) is a USA company product with the following characteristics:

specific gravity 20/20 ° C density (g / cm ³ ) at 20 ° C surface tension (dln / cm 20 Preparation 2 0.98 982 606 At 31 ° C component % By weight 1-NiTro-3- (3-trifluoromethyl-4-fluoro-phenyl) -gyanidine 11.0 sodium hydroxide 2.3 water 86.7 100.0 ' Preparation 3 component Weight% heaven 1- (3-methoxybenzyl) -nitronitroguanidine 11.0 N-pyrrolidone nieíil 57.0 Cs-Cjoalkoholelegy 24.0 Emulphor EL 620 * ^ 8.0 100.0 +) Emulphor EL 620 a GAF Corporation {New

York, New York) polyethoxylated vegetable oil marketed by a US company

Treated plants are grown by methods commonly used for potato test. When they mature (about 20 weeks after sowing), we harvest. The total number of tubers corresponding to size 1 and the total weight of all tubers are determined per plot.

The results obtained were reported in XIX. Table.

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XIX. spreadsheet

Effect on number 1 tubers and on total weight

The number of the preparation and the active ingredient

Number of potatoes per plant

Percentage increase over control Rate of application (kg / ha)

0.5 0.25 0.125 0.0625

First

l- (3,5-Dichlorophenyl) -3- Size 1 +4 + 5 + 6 + 6 nitroguanidine all +4 + 5 + 6 + 6 Second l-Nitro-3- (3-trifluoro Size 1 + 6 + 2 0 +6 methyl-4-fluorophenyl) guanidine all +8 + 3 0 + 6 Third l- (3-methoxybenzyl) -3- Size 1 + 11 + 16 + 8 +9 nitroguanidine all + 11 + 17 +7 + 10

For untreated control, size 1 = 360 pounds / 4046 in ⁵ , total = 390 pounds / 4046 m ²

Example 22

Impact on the total weight of tubers of Russett-Burbank potatoes

The procedure described in Example 21 was followed except that the experiments were conducted in the northwestern United States with vcgrc Russett-Burbank potatoes using the formulations 2 and 3 mentioned in Example 21. The results obtained are shown in Table XX. See Table 1.

Example 23

Increase the total weight of tubers and the number of tubers corresponding to size 1

In the following experiments, the plant growth regulating activity of various compounds of the present invention is investigated for their ability to

XX. spreadsheet

Effect on the weight of tubers in Russett-Burbank potatoes

Number of formulation or active ingredient

Second

1-Nitro-3- (3-trifluoromethyl-4-fluoro-1-phenyl) -guanidine 2

Third

1- (3-Methoxybenzyl) -3-nitro-guanidine 2

Percentage increase over control Rate of application (kg / ha)

0.5 0.25 0,125 0.0625 -3 0 + 14 +6 +8 + 10 +9 + 11 -1 -2 +2 + 11 +6 +14 +4 +2

Size 1 for untreated control = 465 lb / 4046 ni ² , total = 494 lb / 4046 m ²

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Divide 195 637 bulbs by increasing the weight and the number of tubers of size I.

During the experiments Superior potato plants were grown in greenhouses in 30 · 30 · 30 cm boxes. Each box contains two plants and 2 to 2 boxes per treatment. The seedlings were sprayed two weeks after emergence at a rate of 1 kg of application of 0.25% nonionic wetting agent (9 molar ethylene oxide, nonylphenol, oleic acid and isopropanol) in 50% v / v acetone / 50% water. containing solutions. The plants are allowed to mature and harvested. The results obtained are shown in Table XXI. Table.

XXI. spreadsheet

Increase the total weight and the number of tubers corresponding to size 1

Example 24 Effect on increase of sugar yield in sugar beet

In these experiments, sugar beet (Beta vulgaris L.) was sown on open-field plots in the third week of March. The plants are cared for according to conventional methods for sugar beet pulp, with the aid of the

With the difference that 60 or 120 days prior to harvest, the experimental plots were sprayed with an aqueous dispersion of the test compounds formulated as emulsifiable concentrates. When the plants reach maturity, the carrots are harvested and the sugar yield and the purity of the raw sugar juice are determined for each treatment.

The compositions used in these experiments are as follows.

Test compound

The total weight of all tubers in fii ss

Total fresh weight of tubers of size I (% deviation from control)

l- (3-cyanophenyl) -3- nitroguanidine +4 - 3- (3-nhro-guanidine) - benzoic acid methyl ester +5 + 14 l- (3-Ethoxy-fenj.l) -3-nitro- guanidine +1 +8 1- (4-Fluoro-3-methyl-phenyl-3-nitro-guanidine +3 - (3-Difluoromethoxy-phenyl) - 3-nitroguanidine +31 - 1-Nitro-3- (3-2,2,2-trifluoro-1,1-dihydroxyethyl) -phenyl] -guanidine +9 l- (2-Fluoro-5-methyl- henzil) -3-nitro- guanidine + 17 +30 1- (2-Fluoro-5-methoxy) benil) 3-nitro guanidine +9 +26 1- (2-Fluoro-3-methylbenzyl) 3-nitroguanidine +13 +22 l-Nitro-3- (3-trifluoro methoxyphenyl) guanidine +7 + 13

Average untreated control yield: 337 lbs / 4046 m ²

20 Preparation 1 component % By weight of aqueous quantity 25 N-nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine 11.0 N-methyl pyrrolidone 38.0 30 mixture of substituted benzenes (aromatic solvent) 35.0 35 alkylaryl polyoxyethylene glycol, fatty acid and propanol 10.0 octyl-phenoxy-polyethoxy-ethanol (non-ionic surfactant) 6.0 40 100.0 Preparation 2 45 component % By weight quantity 50 l- (3-methoxybenzyl) -3-nittO- guamdin 11.0 N-methylpyrrolidone 38.0 55 mixture of substituted benzenes (aromatic solvent) 35.0 alkylaryl polyoxyethylene glycol, fatty acid and propanol 10.0 60 octyl-phenoxy-polyethoxy-ethanol (non-ionic surfactants) 6.0 65 100.0

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The results obtained are shown in Table XXII. and XXIII. tables.

Experiments have shown that the test compounds are effective in increasing yields of sugars in sugar beet. For example, 1- (3-methoxybenzyl) -3-nitroguanidine, used at a rate of 0.25 to 1.0 kg / ha 60 days prior to harvest, increased sugar yield by 611 kg / ha compared to untreated controls, with a yield of 6130 kg / ha. .

XXII. spreadsheet

Treatment of sugar beet 120 days before harvest

The number of the preparation and the active ingredient Application rate (kg / ha % increase over control sugar crude sugar juice Cleanliness separable sugar First l-Nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine 1.0 + 5 0) +1 0.25 +4 +1 +6 0.0625 +5 +1 +4 Second l- (3-Methoxybenzyl) -3-nitroguanidine 1.0 +3 0 +7 0.25 +3 +1 +4 0.0625 +4 0 +5 Untreated control - 14.49 90.25 18.37 (6818 kg / ha)

XXIII. spreadsheet

Sugar beet treatment 60 days before harvest% increase compared to control

The number of the preparation and the active ingredient Application rate (kg / ha) sugar raw sugar juice flour separable sugar First l-Nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine 1.0 +2 +1 +8 0.25 +2 +1 +2 0,625 +2 +1 +4 Second l- (3-Methoxybenzyl) -3-nitroguanidine 1.0 +3 +1 + 10 0.25 +1 0 + 10 0,625 +1 0 +3 Untreated control __ 14.62 90.17 18.22

(6876 kg / ha)

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Example 25

Yield-increasing effect on Balady garlic (Allium sativum)

During the experiments, 475 kg / ha of garlic seedlings were planted in the open field experiment. 31 days after planting, the seedlings are sprayed with aqueous suspensions of test compounds at a rate of 0.063 0.5 kg / ha.

component % By weight quantity nitroguanidine test compound 11.0 N-methyl-pyrrolidone 38.0 Tenneco 500/100 aromatic solvent * ^ 35.0 T-Mulz 339 Emulsifier Condom Anionic - Nonionic Surfactant ^xx ) 6.0 Multifilm X-77 Spreading Agent ^xxx ) 10.0 100.0

For the meanings of x), xx) and xxx), see Example 21

Six months after planting, the garlic is harvested. The results obtained are shown in Table XXIV. Table.

XXIV. spreadsheet

Effect on yield increase in garlic

Example 26

Investigation of yield-increasing larvae in Chantenay carrot (Daucus carota)

During the experiments, a carrot was sown at a rate of 9 kg / ha. 46 days after sowing, the emerged seedlings contain the active ingredient and 0.25% of the previously identified Multifilm X-77 dispersant 50% v / v on steel and 50% v / v. sprayed with a mixture of water. The plots taken into account for the evaluation include two ridges 0.6 m wide and 10 m long. Nearly four months after sowing, we harvest the beets. The results obtained are reported in XXV. Table.

XXV. spreadsheet

The effect of nitroguanidine derivatives on carotid

Test compound The roots are% by weight of fresh Uses gold íkpfha) increment over control l- (3,5-dichlorophenyl) - 0.5 4-1 3-nitroguanidine 0,125 +6 1 -No ro-3 (3-tri-fluoro- 0,125 + 17 methyl; Fhior-4-nitrophenyl) - 0,063 +26 guanidine 1- (3-Methoxybenzyl) -3- 0.5 +20 nitroguanidine 0,125 + 19

Average yield of untreated control: 26.0 tonnes / ha

The tubers

Use as a percentage of fresh weight

Test compound gold (Kg / ha) increment over control 1- (3,5-Dicyclophenyl) - 0.5 +8 3-nitro-guaniditr 0,125 +5 1-Nitro-3- (3-trifluoro- 0,125 + 13 methyl-4-fluorophenyl) - 0,063 +4 guanidine 1- (3-Methoxybenzyl) -3- 0.5 +9 nitroguanidine 0,125 +8

Average yield for initial control: 17.3 tonnes / ha

Example 27

Investigation of Yield Increasing Effect on Whitc Puiplc Top Globe Brassica Rapa

During the experiments, the test compound was 50 volumes ?? acetone and 50 volumes ?? water-containing dispersions containing 0.25% Multifilm X-77 spreading agent. 8 or 12 weeks after sowing, the experimental composition is applied to the white beet foliage in a post-emergence manner, i.e. after emergence. The plots taken into account for the evaluation include a 3.3 m long furrow arranged on a 100 cm heap of land. Six repetitions are performed per treatment. The carrots will ripen for four months after sowing! we harvest. The results obtained are shown in Table XXVI. Table.

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XXVI. spreadsheet

Yield increasing effect on white beet

Λ AT //. spreadsheet

Investigation of yield increasing effect on beetroot

Test compound Λ roots fresh Usage weight% The proportion (Kgflia) increment over control 10 1- (3-Methoxybenzyl) - 2.0 +5 3-nitroguanidine applied 8 weeks after sowing (root thickness 1.25-2.5 cm) 0.5 +3 15 1- (3-Methoxy-benzyl) - 2.0 +29 20 3-nitroguanidine applied 12 weeks after sowing (root thickness 3.8-7.5 cm) 0.5 +5 25

Experimental blend Λ% of fresh root use by weight gold (Kg (IIa) increment over control 1- (e-Methoxybenzyl) - 2.0 +13 3-nitroguanidine 0.5 +5 applied 8 weeks after sowing (root thickness 7.5-15 cm) l- (3-Methoxy-benzyl) -3 2.0 + 14 nitroguanidine 0.5 -2 12 weeks after sowing applied at (Root thickness 20 -40 cm)

Average yield of untreated control: 332 lbs / 4046 cm ²

Example 28

Investigation of the yield-enhancing effect of Green Top Bunching Beetroot (Beta vulgaris) 35

The procedure described in Example 27 was followed except that beet was used as a pilot plant instead of white beet. The result obtained is two in the XXVII. Table.

Example 29

Investigation of yield increase effect on Iverson variety Tulipa sylvestris

During the experiments, the tulips growing in the open air are treated when almost 100% of the tulips are pollinated or when they are all in late flowering. Plants were treated with test compound compositions containing 20% (v / v) acetone containing 0.25% Multifilm X-77 spreading agent. During the experiments, the plot size is such that it contains one row of about 1.65 meters in length. Each experiment was repeated six times. The results obtained are shown in Table XXVIII. Table.

XXVIII. spreadsheet

Investigation of yield increasing effect on tulips

Large tubers fresh Big tubers Test compound Utilization rate by weight number (Kg / ha) % increase over control l- (3-Methoxybenzyl) -3-nitroguanidine 2.0 +26 +35 (100% budding) 0.5 +80 +81 l- (3-Methoxybenzyl) -3-nitroguanidine 2.0 0 +5 (full bloom) 0.5 +53 +49

-3 059

Example 30

Investigation of Yield Effect on Dohlgren D0164 Sunflower (Helianthus annus)

In this series of experiments, sunflower growing in 18 cm pots placed in rows 75 cm apart is treated with an aqueous dispersion of the test compound in the so-called growth states V8, VI1-12, V-16, V20 (R1) or V22 (R2-5). The test compounds were dispersed in a 2: 1 mixture of acetone and water containing 0.25% nonionic wetting agent (i.e., a mixture of nonylphenol, oleic acid and isopropanol containing 9 moles of ethylene oxide). The dispersions are applied as an aqueous spray in amounts sufficient to provide a rate of application of 0.31 kg / ha based on experimental results. Five months after sowing, the heads containing the seeds are harvested and the weights of the seeds are determined for each plant. The results obtained in the XXIX. Table.

they are sprayed with aqueous dispersions of test compounds previously formulated as liquid concentrates. The liquid concentrates used are concentrates containing 30% by weight of 1- (3,5-dichlorophenyl) -3-nitroguanidine, 0.4% by weight of colloidal magnesium aluminum silicate, 1.5% by weight of naphthalene-foraldehyde. condensate, 8 wt% polyethylene glycol, 0.1 wt% nonylphenolethylene oxide condensate (9-11 moles ethylene oxide), 0.1 wt% sodium lignosulfonate, 0.07 wt% citric acid, It contains 06% by weight of xanthan gum, 59.67% by weight of water and 0.10% by weight of paraformaldehyde. Λ Dilute the liquid concentrate with water and add 0.25% w / w Multifilm X-77 dispersant in a spray tank. The resulting dispersion was sprayed onto the vegetation at a rate of application of 0.25 kg / ha. The plants are harvested after ripening. Λ results obtained 3

XXX. are summarized in Table. It should be noted that as a result of the treatment of tobacco plants, the aging of the lower tobacco leaves is delayed and thus it is possible to harvest all the leaves simultaneously with a single cut.

XXIX. spreadsheet

Investigation of yield increasing effect on sunflower

The fresh Usage mass of the seeds

Increment of test compound ratio (kg / ha) to control-capable * 1- (3,5-Dichlorophenyl) 3-nitroguanidine applied to subsequent vegetative stages

V8 0.31 +17 VII-12 0.31 +37 V16 0.31 +29 V20 (R1) 0.31 +26 V22 (R2-5) 0.31 +5

XXX. spreadsheet

Yield increasing effect on tobacco

examination Test compound Application gold (Kg | ha) Increase in dry weight of leaves compared to control

- (3,5-Dichlorophenyl) 3-nitroguanidine at the following height:

5 cm 0.25 +38 45 cm 0.25 +64 15 cm 0.25 + 112

Example 31

Investigation of Yield-Increasing Effect of Coker 319 Tobacco (Nicotiana tabacum)

In this series of experiments, Coker 319 tobacco plants are grown in 22.5 cm plastic pots, one plant per pot. Λ Place the pots in rows 50 cm apart and perform 4-6 repetitions per treatment.

When plants are 5, 45 or 115 cm in height

Example 32

Investigation of yield increasing effect on Italian Red onion (Allium cepa)

In this experiment, bulbs are planted in the open air every 10 cm. The experimental plots included in the evaluation consist of two 0.6 meter wide and 10 meter revenge ridges. 37 days after planting, the experimental plots were sprayed with a dispersion of one of the formulations described below.

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Preparation 1

Component% by weight % By weight quantity l- (3,5-dichloro-phenyl) -3- nitroguanidine 11 Tcnncco 500/100 aromatic solvent 35 T-Mulz 339 emulsifier 6 Multifilm X-77 spreading agent 10 N-methylpyrrolidone 38 100

Preparation 2

component % By weight quantity l- (3-methoxycarbonyl-benzyl) -3-nitro- guanidine 11 Tenneco 500/100 aromatic solvent 35 T-Mulz 339 emulsifier 6 Multifilm X-77 spreading agent 10 N-methylpyrrolidone 38 100

Four months after treatment, the onions are harvested. Λ got results in XXXI. Table.

XXXI. spreadsheet

Onion yield enhancing effect

Cmu per tin)

Use fresh weight

Increase in test compound ratio (kg / ha) compared to control

1 (3,5-Dichlorophenyl) - 0.5 +32 3-nitroguanidine 0,125 +22 1-Nitro-3- (3-trifluoro- 0,125 + 25 methyl-4-fluorophenyl) - 0,063 +32 guanidine 1 - (3-Mct0xi-bcn7.il j-3- 0.5 +21 nitroguanidine 0,125 + 23

Untreated control! average yield: 177 g / tuber

Example 33

Investigation of Yield Increasing Effect of Yellow Beetroot (Brassica napus) on Napobrassica

The yield enhancing effect of the test compounds on the yellow carrot is investigated as follows. The carrots will be planted in early May. Two months later, they are sprayed with aqueous dispersions of the test compound in the liquid concentrate of Example 31. Harvest four months after planting. The results are shown in XXX11. Table.

XXXII. spreadsheet

Preparation 3 component % By weight quantity 1-nitro-3- (3-trifluoromethyl-4-fluoro-phenyl) -guanidine 11 Tenneco 500/100 aromatic solvent 35 T-Mulz 339 emulsifier 6 Multifilm X-77 spreading agent 10 N-methylpyrrolidone 38 100

Harvesting effect on turnips

Test compound 1 · \ Ί benefit famous gold (Kg / ha) Répánként! I'riss is the increase in weight compared to the control 1-Nitro-3- (3-trifluoro- 0,125 +54 methyl 4-fluoro-phenyl) - 0.5 +3 guanidine 1- (3,5-Dichlorophenyl) - 0,125 +39 3-nitroguanidine 0.5 +3 1- (3-Methoxybenzyl) - 0,125 + 19 3-nitroguanidine 0.5 +8

Average yield of untreated control: 510 g / beet

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XXXIV. spreadsheet

Example 34

Investigation of yield increasing effect of Saranoc alfalfa (Medicago sativa)

During the experiments, the test compounds were treated with an aqueous dispersion of 12.5 cm x 12.5 cm glass shaker preemergently seeded with alfalfa seeds. Each bowl contains four plants and each treatment is performed in five repetitions. The test compounds were used in the form of a 1: 1 mixture of acetone and water containing 0.25% by weight of a nonionic wetting agent (a mixture of nonylphenol, oleic acid and isopropanol containing 9 moles of ethylene oxide). The treatment is carried out in the first flowering stage of growth. Six weeks after spraying, the alfalfa is cut off and the alfalfa stems are counted per dish. The results obtained are shown in Table XXXIII. Table.

XXXIII. spreadsheet

Lucerne has a yield increasing effect

Experimental compound Application rate (kg / ha) Number of stems per bowl l- (3,5-dichlorophenyl) - 0.06 11.8 3-nitroguanidine 0.03 12.4 0,015 14.4 0.0075 14.8 Untreated control - 11.2

Example 35

Investigation of terinine yield increasing effect in tomato (Lycopersicon esculentum)

During the experiments, tomatoes were planted in beds of two rows, spaced 45 cm between each row. The experimental plots contain two rows of 6 meters each. The plots are sprayed with aqueous dispersions of the test compounds when the plants first bloom. The test compounds are used in the form of the compositions described in Example 32. The aqueous dispersions prepared from these are utilized at a rate of application of 1.0 kg / ha. The results are determined when the tomato begins to ripen. The results obtained are shown in Table XXXIV. Table.

In the case of tomatoes, the yield-increasing effect

Experimental compound Application gold (Kg / ha; 6 inches long rows on Inrlalinazing bed Quantity of parsley tomatoes (kg) Untreated control - 106.8 l- (3-methoxy-benzyl) - 3-nitroguanidine 1.0 113.8 Example 36

Yellow daffodils.

Examination of the slowing down of the opening in cut flowers (Nnrcissiis pscudonareissus)

Λ Experiment In the morning, we collect yellow daffodils with fully opened buds. The stems are cut back to 30 cm annoyance, and within one and a half hours of collection, the stems of flowers are dipped in 200 ml of the test compound solution at a depth of 10 cm. The solution of the test compound was 100 p.p.m. concentration. Prepare by dissolving 100 mg of 1-nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine in 100 ml of acetone and adjusting the volume to 2000 ml in deionized water. The control solution is water containing only 5% by volume of acetone.

After immersing in the test solution for 3 minutes, 30 minutes, 90 minutes, 270 minutes or 24 hours, a blank sample is transferred to 0.5 liter wide mouth amber vessels containing 450 ml deionized water. These samples are kept in these vessels until the end of the experiment. However, three samples are kept in the experimental solution until the end of the experiment. The control flower samples were kept in water containing 5 volumes of acetone for 30 minutes and 24 hours (3 -3 samples for each dip time) and placed in deionized water. 3 samples were kept in deionized water for the duration of the experiment. The treated dishes were randomly distributed in a laboratory at about 21 to 25 ° C. Λ natural sunlight supplemented with fluorescent light to provide a 12-hour bright day,

The decorative value of the flowers is evaluated two days and four days after treatment. Each sample is evaluated individually for the appearance of the perianthium and the crown-like crop on the following scale, with increasing numbers representing decreasing aging. Finally, each treatment is assigned an unweighted average representing the overall appearance of the flower.

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Decorative acceptability Numeric Description

Decorative Acceptance Numbers Description

A) shroud

acceptable 1 fresh appearance, sheath is smooth and 5 unacceptable 7 completely dry and / or brown · smooth, no visible sign B) crown-like fruit overripe 10 acceptable 1 straight keeping! and concise acceptable 2 slight curling at the edges acceptable 2 expanding and fading acceptable 3 slight wilting 15 acceptable acceptable 3 slight wilting, 4 marginal pre- edges discolored coloration (staring) and incgnövckcdctt (brown) wilting 20 unacceptable 4 less than half withered unacceptable 5 in less than half of the veil and / or brown (withered) pigment (Transparency) 25 unacceptable 5 more than half withered and / or unacceptable 5 the shroud is more than brown (withered)

Half the loss of pigment (transparency)

XXXV. spreadsheet

100 p.p.m. over different time periods Freshness of yellow daffodils treated with 1-nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine

Experimental Compound ^The freshness of the ^dip Flower lasts from two days to four days after treatment

l-Nitro-3- (3-methyl-trifhior-4-fluoro-phenyl) -guanidine 3 minutes 30 minutes 90 minutes 1.8 1.7 1.7 2.5 2.5 2.7 270 minutes 24 hours 1.3 2.2 complete experiment 1.5 2.7 acetone control 30 minutes 2.2 3.5 acetone control 24 hours 2.3 3.8 water control complete experiment 2.2 3.3

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The test is continued after the flowers have lost their fresh, floral-like decorative value in order to observe the stems. (Stcddart, JL, page 1 of the British Plant Growtb Regulator Group, Monograph 8, defines plant aging and thinning as follows: ') The retention of chlorophyll in the stems (or stems) of the flowers of the yellow daffodil, when treated with the compounds of the present invention, indicates delayed aging after the untreated stems lose their chlorophyll content, i.e. yellow or brown.

In this series of experiments, flower stalks are evaluated for color and overall appearance 17 days and 25 days after treatment. The stems of the flowers are individually evaluated for color and swelling and assigned numerical values (see Table XXXVI). Increasing numerical values are associated with increasing decreases in photosynthetic capacity, increasing chlorophyll depletion, and structural; refers to a loss of moral integrity, meaning that, in summary, increasing overripeism results in death.

Scale for measuring the ripeness of the stalk (pumpkin) of the yellow daffodil

5 numerically value Dominant color and appearance 10 i green, swollen, meaning little or no sign of overripe 2 greyish green, swollen, ie slight overripe 15 3 yellowish-green, swollen 4 yellow, swollen 20 5 yellowish-brown, swollen, ie advanced overripe 6 brown, stiff, ie complete overripe 25 7 brown, collapsed, destroyed

XXXVI. spreadsheet

100 p.p.m. over different time periods Delayed overripe of yellow daffodils treated with 1-nitro-5S-trifluoromethylA-fluorophenyl] guanidine

Test compound Duration of immersion Λ stalk color and appearance after treatment 17 days 25 days l-Nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine 3 minutes 1.3 1.3 30 minutes 1.0 2.0 90 minutes 1.3 4.0 270 minutes not rated 1.0 24 hours 1.3 5.3 complete experiment 4.0 7.0 5% acetone control 30 minutes 4.7 7.0 5% acetone control 24 lira 5.7 7.0 water control complete experiment 5.3 7.0

Example 37

Yield study on lucerne yield, The experiments described in Example 34 were repeated, except that the test compound was applied at a rate of application of 3.5 g / ha to 20 g / ha of 1- (3,5-dichlorophenyl) -3-nitro- guanidine is used. Experimental results in% deviation from control (relative to dry weight of alfalfa) are reported in XXXVII. Table.

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XXXVII. spreadsheet

Lucerne has a yield increasing effect

Growth of experimental compound of dry weight of Lucerne relative to control

Untreated control - 1- (3,5-Dichlorophenyl) 3-nitroguanidine 20 g / ha +8.0 15 g / ha +20.0 7.5 g / ha +39.0 3.5 g / ha +25.0

Example 38

Investigation of tcrm and yield increasing effect in apples

During the experiments, the test compounds were prepared in a mixture of 50% v / v acetone and 50% v / v water at 0, 10, 100 or 1000 p.p.in. in the form of aqueous dispersions or solutions containing the active ingredient and about 0.25% (v / v) nonionic wetting agent (containing 9 moles of ethylene oxide in nonylphenol, oleic acid and isopropanol). The dispersions to be tested are applied to apple trees of the Super Delicious Oregon species (Malus sylvestris) in spring at the peak of flowering. Each experimental solution was sprayed until spillage. For each treatment, two trees are utilized and randomly selected from a group of individuals in the same flowering state. During further growth, the experimental plantation is treated in a conventional manner, utilizing the conventionally used fungicides and insecticides. At the end of the season, fruits are harvested from each tree, weighed and the average weight of each tree is determined. The results obtained are shown in Table XXXVIII. Table.

XXX Fruit. spreadsheet

Yield increasing effect on apples

Experimental compound Application gold (Ppm) Average yield per tree (kg of fruit) l- (3,5-dichlorophenyl) - 1000 25.88 3-nitroguanidine 100 27.68 10 28.04

Test compound Application gold (Ppm) F'.gy average yield (kg fruit) control 0 17.69 l- (3-Methoxy-beiizilj- 1000 16.34 3-nitroguanidine 100 28.26 10 26.33 control 0 21.38

Example 39

Prolongation of freshness in Mangold

Slow down the wilting of the chard leaves by dipping the leaves for a short time at 8 p.p.m. and 512 p.p.m. in experimental solutions containing the active ingredient in the form of solutions of 1- (3-methoxybenzyl) -3-nitroguanidine in acetone. The leaves of mangold plants grown in the open air are cut and each is cut in half along its length. One half is immersed in the test solution for 60 seconds, while the other half is immersed in a mixture of water and an appropriate amount of acetone for 60 seconds (no effect of acetone alone). The leaf pieces are dried and placed on trays containing a wet towel. The mice were kept at 20 ° C for four days, and the trays were kept at 30 ° C for a further four days. Aging is assessed visually by monitoring for loss of chlorophyll and / or development of leaf necrosis. The effective concentration range is 8 to 64 p.p.m.

Treatment (p.p.m.) 1-13-Methoxybenzyl Aging Delay (control)

As a percentage of 3-nitroguanidine)

0

25

70

512 75

Example 40

Extending the freshness period for cut gladiolus flowers

For cut flowers, the duration of freshness is given by the so-called vase time, which is the period during which the flower retains its decorative value. The vase time is partly determined by the ability of the stalk to be cut, that it can still absorb nutrients and water to keep the flower fresh. This ability is especially important for flowers whose stems have many flower stems. An example of such a flower is gladiolus. If such flowers have not yet opened

-36195 637 buds (these buds may open in the vase) and if the bud opening is acropetal over time, the maximum vase time will depend in particular on the existence of a viable stem.

Gladiolus flowers are picked up from a local florist and delivered to the laboratory in the form of a commercially packaged box. The stems are cut back to 30 cm in a cold room at 4 ° C and 60% relative humidity and then immersed in a treatment solution of the following composition:

Component g / liter

saccharose 20.00 citric acid monohydrate 4.20 8-hydroxyquinoline citrate 0.20 deionized water nearly 900 ml

Decorative Number Acceptance Value

Description

5 2.5 moderate withering with slight staring at the edges accept- 3 advanced wilting 10 useless 3.5 cs staring severe wilting, staring as some areas dry up 15 4 complete withering and dehydration

the pH is then adjusted to 4.6 with 10 mol / l potassium hydroxide solution (about 3.9 ml / l solution) deionized water 1000 ml / l

An additional evaluation is made to express the degree of wilting and the proportion of faded flowers on the following scale.

Evaluation of freshness of cut gladiolus Percentage of wilting of flower buds

Decorative acceptability

Percentage of faded flowers

The vases containing the flowers are randomly placed in the laboratory at 21-25 ° C. The natural light is replaced by fluorescent light to provide 12 hours of light per day. If necessary, the medium is supplemented.

The flowers are evaluated for their decorative value 5 days after treatment. 5-5 stems for each repeat and 2-2 repetitions for each treatment. On each stalk, a single value is assigned to the overall appearance of each open flower, determined on the following scale. (The increasing number on the scale indicates increasing aging.) Acceptable unacceptable

0-10

10-25

25-50

50-75

75-100

100

Evaluation of freshness of cut gladiolus

The severity of the flower buds staring and staring

The number of buds that open at least 1 cm / cm and the color of the buds are recorded without open flower buds and healthy bud buds, i.e. petals without visible discoloration, discoloration and turgor (swelling). The color change that accompanies aging is indicated by the following markings.

Evaluation of freshness of cut stadiums by color

Decorative Acceptance Value is acceptable fresh, no wilting

1.5 traces of wilting (shrinkage), slight edges of curled edges

Evaluation Color Dk gn dark green gn green YG yellowish green Y yellow Br brown

Increasing aging

The results of these experiments are shown in Table XXXIX, 65.

-37195 637

XXXIX. spreadsheet

Increased vase time of cut gladiolus flowers 100 p.p.m. after treatment with solutions containing the active substance

Treatment Open floret pity Open buds Iá Flowering of flowers Shit liervadása Shit color Bud Rate (%) Seriousness unshaven (DIW) 19 5 50-75 3.0 medium Y6 Y6 / Br control (DIW) 25 9 10-25 2.5 mild YG / Gn YG / Gn control (Ac) 21 11 10-25 2.5 mild YG / Gn Y6 1-Nitro-3- (trifluoromethylphenyl) guanidine 23 42 0 1.0 - Dk Gn gn 1- (3,5-dichlorophenyl) 3-nitroguanidine 49 15 0 1.0 - Dk Gn gn 1-Nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine ¹ , 17 37 0 1.0 Dk Gn gn l- (3-methoxybenzyl) - 3-nitroguanidine 42 21 0 1.0 NRL Dk Gn gn AOAA 18 35 0-10 1.5 - Dk Gn gn

It can thus be seen that if the flowers of the cut gladiolus are treated by immersing the stems in a solution of the substituted nitroguanidines of the invention for 30 minutes, the vase time of such flowers is significantly longer than that of the untreated flowers. The resultant growth can be judged by a number of criteria, including an increase in the number of acceptable open petals, a reduced degree and severity of wilting of the petals, an increased retention of the green of the stems and buds and an increased retention of the stalks. 45

Example 41

Examination of delayed aging in leafy vegetables 50

We buy kale and American kale in the local market and store it in a plastic bag in the refrigerator until use. The outermost leaves are discarded and young, healthy, intact leaves are used for experiments. The leaves are separated from the stem by cutting them off with a sharp scalpel at the connection point. Immediately after cutting, 'leaf stalks are placed in the treatment solutions. The latter are filled into wide-mouth amber containers of approximately 100 ml. In order to keep the leaf and to minimize the evaporation loss of the treatment solution, the dishes are plugged with plastic foam stoppers that have been pre-scalpeled to receive the leaf handle.

100 p.p.m. Prepare a concentrated solution of this solution by dissolving 200 mg of 1-nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine in 100 ml of acetone and adjusting the final volume of the resulting solution to 2000 ml with deionized water. Treatment solutions of 10 ppm and 1 ppm, respectively, were prepared in 10-fold dilutions using 5% acetone in water as diluent, and pure water and 5% acetone in water were used as controls.

For both kale and American kale, each treatment is done in quadruplicate, and leaves from different plants are used for each replicate. The dishes were then randomly placed in a laboratory at 21-25 ° C. Natural light is complemented with fluorescent light to provide 12 hours of light per day. If necessary, the treatment solutions are replaced by a funnel whose stem extends into the vessel through the radial cut of the plastic foam stopper. At 1, 3, and 7 days after treatment, the leaves are evaluated for green and the following values are assigned.

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Numeric values Color Increasing aging dark green green light green beige yellow brown

The mean values obtained from each treatment on observation days are reported in XL. table.

component Töineg% naphthalene formaldehyde condensate 1.5 polyethylene glycol 8 Nonylphenol ethylene oxide condensate containing 9 to 11 moles of ethylene oxide 0.1 Sodium lignosulphonate 0.1 citric acid 0.07 water 46 xanthan resin 0.06

XL. spreadsheet

Effect on Kale and American Kale Concentration of l-nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine (p.p.m.)

Leaf color 1, 3 and 7 days after treatment kale American cabbage.

1 3 7 1 3 7 100 1.0 1.0 1.8 1.0 1.1 2.8 10 1.0 1.0 1.0 1.0 1.0 3.5 1 1.0 1.0 2.0 1.0 1.3 3.7 0 (5% acetone) Shoot 1.0 5.3 1.0 2.3 4.5 0 (DIW) 1.0 2.0 5.3 1.0 3.3 3.8

These results clearly justify the delay in the onset of fading in the treated leaves.

Example 42

Preparation of Liquid Concentrate The following components are ground:

component

Crowd%

Example 1 Compound 46 Colloidal Magnesium Aluminum Silicate 0.4

Example 43

Moisturizable powder preparation Λ the following components are crushed: component Crowd% Example 1 80 kaolin 10 Sodium lignosulfonate 5 octylphenoxy polyethoxy ethanol 5

Claims

Claims (4)

Claims 1. Yield and plant growth A regulatory composition comprising from 0.001% to 80% by weight of an nitroguanidine derivative of formula (V) 50 W _s is hydrogen, fluorine or chlorine, X ₅ is hydrogen or hydrogen Alkyl having 1 to 4 carbon atoms, -CN, -NO ₂ , CH ₂ CN, -OCF ₂ ClIF ₂ , -OCF ₃ , -CF ₃ , C 14 alkoxy, tetralidro-211 ⁵⁵ pyran-2-ϋ, - C (OH) ₂ CF ₃ , -SCH ₃ , -COCH ₃ , -N (CH ₃ ) ₂ , -COOCH ₃ or -CH ₂ OR ₃ , with the latter being R ₃ -CH ₂ OR ₃ , and with the latter being R ₃ -CII ₃ , Y ₅ is hydrogen or halogen or ⁶⁰ -CH ₃ , Z _s is hydrogen or halogen -CH ₃ , -OCH ₃ or -CF ₃ , R ₄ is hydrogen or -CH ₃ , -C ₂ H _S 65 or ~ ^CF 3 groups, -39195 637 R _s is hydrogen or -CII _3, R _o is - NO _2, or CN, m is 0 or 1, and n is 0 or 1, - or any of these tautomcrjél or alkali metal salt thereof, and a solid or liquid, organic or inorganic an inert carrier, preferably magnesium aluminum silicate or N-methyl-pyrrolidone and optionally a nonionic, anionic or cationic surfactant, preferably a dispersing or emulsifying agent, preferably sodium phenol-phenoxyethoxyethane or octylphenoxy-polyethoxyethane; containing ethanol in a total amount of 100% by weight. 2. A composition according to claim 1 wherein the active ingredient is 1-nitro-3- (3-trifluoromethyl-4-fluorophenyl) guanidine, 1- (3,5- dichlorophenyl) -3-nitroguanidine, 1-nitro- (3-trifluoromethylphenyl) guanidine, 1- (3-acetylphenyl) -3-nitroguanidine, 1- (3-difluoromethoxyphenyl) - Contains 3nitroguanidine or mixtures thereof. 3. A composition according to claim 1 wherein the active ingredient is 1- (3-methoxybenzyl) -3-nitroguanidine, 1- (2-fluorobenzyl) -3-nitro- guanidine, 1- (2-fluoro-5-methoxybenzyl) -3-nitroguanidine, 1- (4-fluorobenzyl) -3-nitroguanidine, or mixtures thereof. 4. A process for the preparation of a compound of formula (V): wherein W ₅ is hydrogen, fluorine or chlorine, X _s represents hydrogen, halogen, alkyl of straight or branched C 1-4 carbon atoms, -CN, -NO _2, -CI1 ₂ CN, -OCF ₂ CHF _2, -OCF _3, -OCHF _2, -CF _3, C 14 -alkoxy, -COOH, -NH ₂ , -ClU-COOClHs, -CH ₂ -N (CH ₃ ) ₂ , tetrahydro-2H-pyran-2-yl, -OH, -C (OH) ₂ CF ₃ , -SCH ₃ , -OSO ₂ CH ₃ , -N (CH ₃ ) ₂ , -COCH ₃ , -COOCH ₃ or -CH ₂ OR ₃ , in which R _{3 is} hydrogen or -CH ₃ , Y ₅ is hydrogen, halo or -OH ATON, OC1I _3, CH _3, CF ₃ CHF, CII ₂ COOH, -OCF _{2 2)} -OC _3, -CH ₂ -N (CH _{3) 2,} -CH ₂ NH ₂ , -CN, - NHCOCH3 or -N (C ₂ H _s ) ₂ , or X ₅ and Y ₅ together form -0 C11 ₂ O-, Z _s is hydrogen or halogen _-CH3, -OCI1 ₃ or -CF ₃ group, R ₄ is hydrogen or -CH ₃ , -C ₂ H ₅ , -CF ₃ , phenyl or benzyl, R _s represents a hydrogen atom or -CH ₃ group, R ₆ is -NO ₂ or -CN, m is 0, 1 or 2, and n is 0 or 1 for the preparation of their tautomers and their alkali metal salts, (a) nitro-guanidine derivatives of the general formula (V) forming a narrower group of compounds of formula (V): Xj is halogen or -COCII ₃ , -CN, -CH ₂ CN, -C (OH) ₂ CF ₃ , -OCHF ₂ , -OCF ₃ , -CH ₃ , -SCH ₃ , -CF _3i -COOH, -NH ₂ , -CH ₂ -COOC ₂ Ih, -CH ₂ -N (CH ₃ ) ₂ , OSO _{2 is} CII ₃ , NO ₂ , OCF ₃ ClF ₁ , ocyl ₃ , -N (CII ₃ ) ₂ , COOC 11 ₃ or C ₁₂ OR ₃ , and in the latter R _{3 is} hydrogen or -CH ₃ , Y [represents hydrogen or halogen or -CH ₃ , CF ₃ , -CH ₂ -COOH, -OCF ₂ CHF ₂ , -OCH ₃ , -CH ₂ -N (CH ₃ ) ₂ , -ch ₂ n h ₂ , -cn , -NHCO ₂ CH ₃ or -N (C ₂ H ₅ ) ₂ , or Xi and Y! together form -O CH ₂ O-, Z (represents hydrogen or haloatomine or -CH _3, -OCR _3, or -CF ₃ group, R is hydrogen or -CH ₃ with the proviso that when (i) when Xi is fluoro, chloro or bromo, or -CH ₃ or -OCH _3, and Rj is hydrogen then Y and Zj are simultaneously hydrogen. and (ii) when Xt is a chlorine atom and Zj and R are both hydrogen, then Yj is other than methyl - to produce a compound of formula VI wherein X, Y _t and Z j are as defined above, an equimolar amount of a compound of formula VII wherein R 'is a C 1 -C 4 alkyl group in aqueous alcoholic solution, the reaction mixture is heated to about 40 ° C, treated with a strong base and the alcohol is removed, then the residue is acidified and In this case, it is treated with methyl iodide and silver oxide to form a product containing R; let's go, or (b) nitro-guanidine derivatives of formula (II) which form a narrower group of compounds of formula (V): X- is hydrogen or halo, or -O 11 straight or branched C 1-4 alkoxy, -SCH ₃ , -OCF ₃ , -CF ₃ , straight or branched C 1-4 alkyl, 6 -oxacyclohex-1-yloxy or tetralidio-211-pyran-2-yl, Y ₂ is hydrogen or fluoro, Z ₂ is hydrogen or fluorine or -CH ₃ or -OCH ₃ , W 1 is hydrogen or fluorine, m is 0, 1 or 2, R ₂ is hydrogen or -CH ₃ , -C ₂ H ₅ , -CF ₃ , phenyl or benzyl, provided that (i) when m is 0 and R _{2 is} hydrogen or -CII ₃ , then W ₂ , X ₂ . Y ₂ and Z _{2 have the} same meaning other than hydrogen, and (Ii) when m is 1, R ₂ , W ₂ , X ₂ , Y ₂ and Z ₂ at the same time represent a compound of formula (XI) - other than hydrogen - wherein W ₂ , X ₂ , Y ₂ , Z ₂ and R ₂ are as defined above, m is 0, 1 or 2, n is 0 or 1-nitroguanidine in a solvent, preferably water, and the reaction mixture is maintained at 50-75 ° C for 1 hour, or c) a cyanoguanidine derivative of the general formula (III) which is a narrower group of compounds of the formula V: X ₃ represents a halogen atom or -0CH _3, -CH ₃ or -CF ₃ group, Y ₃ is hydrogen, halogen or -OH, and Z ₃ is hydrogen or chlorine, with the proviso that (i) Y ₃ and Z ₃ can simultaneously represent i hydrogen when X ₃ is -OCII ₃ , and (ii) X ₃ and Y ₃ are both chloro, are bromo or iodo, then R Z ₃ is not H, and (iii) when X ₃ CII -CH ₃ and Z ₃ is hydrogen, then Y ₃ is a chlorine atom - the preparation of formula (XII) with a compound of the formula: - wherein X _3, Y ₃ and Z ₃ are dispersed in a strong acid as defined above and the reaction mixture thus obtained is mixed with at least an equimolar amount of an aqueous solution of sodium dicyanamide, or d) cyano-guani10 din derivatives of the general formula (V) which form a narrower group of compounds of the formula V: W ₄ is hydrogen or fluoro, and X ₄ is hydrogen, fluoro, or straight or branched C 1-4 alkoxy or straight or branched C 1-4 alkyl, provided that when W _{4 is} fluoro means then 2θ X ₄ is hydrogen, dispersing a compound of formula XIII in which X 1 and W ₃ are in the previously defined strong acid, and mixing the resulting reaction mixture with an aqueous solution of at least an equimolar amount of sodium dicyanamide, and optionally converting the product of one of the processes a) to d) into an alkali metal salt.